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The evolution of the prebiotic atmosphere.

One-dimensional radiative convective and photochemical models are used to estimate the vertical temperature structure and composition of the earth's prebiotic atmosphere. Greatly enhanced CO2 levels (100-1000 times present) are required to keep the mean surface temperature above freezing in the face of decreased solar luminosity during the earth's early history. Such high CO2 partial pressures would have affected the atmospheric oxidation state by facilitating the photochemical production of soluble species including H2O2 and H2CO. Oxidation of ferrous iron in the oceans by H2O2 dissolved in rainwater should have kept the atmospheric H2 mixing ratio above 2x10(-4) and the ground-level O2 mixing ratio below 10(-11), regardless of the magnitude of the rate of volcanic release of reduced gases.

Atmosphere↗

The search for other planets: clues from the solar system.

Studies of element abundances and values of D/H in the atmospheres of the outer planets and Titan support a two-step model for the formation of these bodies. This model suggests that the dimensions of Uranus provide a good index for the sensitivity required to detect planets around other stars. The high proportion of N2 on the surfaces of Pluto and Triton indicates that this gas was the dominant reservoir of nitrogen in the early solar nebula. It should also be abundant on pristine comets. There is evidence that some of these comets may well have brought a large store of volatiles to the inner planets, while others were falling into the sun. In other systems, icy planetesimals falling into stars should reveal themselves through high values of D/H.

Astronomical Phenomena↗

The D/H ratio and the evolution of water in the terrestrial planets.

The presence of liquid water at the surface of the Earth has played a major role in the biological evolution of the Earth. None of the other terrestrial planets--Mercury, Venus and Mars--has liquid water at its surface. However, it has been suggested, since the early seventies, from both geological and atmospheric arguments that, although Venus and Mars are presently devoid of liquid water, their surfaces could have been partially or completely covered by water at some time of their evolution. There are many possible diagnostics of the long-term evolution of the planets, either from the present characteristics of their surfaces or from their present atmospheric compositions. Among them, the present value of the D/H ratio is of particular interest, although its significance in terms of long term evolution has been challenged by some authors. Recent progress has been made in this field. We now have evidence for higher D/H ratios on Mars and Venus than on Earth, with an enrichment factor of the order of 5 on Mars, and about 100 on Venus. Any scenario for the evolution of these planets must take this into The most recent models on the evolution of Mars and Venus are reviewed in light of these new measurements.

Atmosphere↗

Archean geochemistry of formaldehyde and cyanide and the oligomerization of cyanohydrin.

The sources and speciation of reduced carbon and nitrogen inferred for the early Archean are reviewed in terms of current observations and models, and known chemical reactions. Within this framework hydrogen cyanide and cyanide ion in significant concentration would have been eliminated by reaction with excess formaldehyde to form cyanohydrin (glycolonitrile), and with ferrous ion to form ferrocyanide. Natural reactions of these molecules would under such conditions deserve special consideration in modeling of primordial organochemical processes. As a step in this direction, transformation reactions have been investigated involving glycolonitrile in the presence of water. We find that glycolonitrile, formed from formaldehyde and hydrogen cyanide or cyanide ion, spontaneously cyclodimerizes to 4-amino-2-hydroxymethyloxazole. The crystalline dimer is the major product at low temperature (approximately 0 degrees C); the yield diminishes with increasing temperature at the expense of polymerization and hydrolysis products. Hydrolysis of glycolonitrile and of oxazole yields a number of simpler organic molecules, including ammonia and glycolamide. The spontaneous polymerization of glycolonitrile and its dimer gives rise to soluble, cationic oligomers of as yet unknown structure, and, unless arrested, to a viscous liquid, insoluble in water. A loss of cyanide by reaction with formaldehyde, inferred for the early terrestrial hydrosphere and cryosphere would present a dilemma for hypotheses invoking cyanide and related compounds as concentrated reactants capable of forming biomolecular precursor species. Attempts to escape from its horns may take advantage of the efficient concentration and separation of cyanide as solid ferriferrocyanide, and most directly of reactions of glycolonitrile and its derivatives.

Acetonitriles↗

Hydrothermal and oceanic pH conditions of possible relevance to the origin of life.

Because of the continuous focusing of thermal and chemical energy, ancient submarine hot springs are contenders as sites for the origin of life. But it is generally assumed that these would be of the acid and high-temperature 'black smoker' variety (Corliss et al., 1981). In fact today the greater part of the ocean circulates through off-ridge springs where it issues after modification at temperatures of around 40 degrees C or so but with the potential to reach 200 degrees C. Such offridge or ridge-flank springs remind us that there are other candidate sites for the origin of life. Although there is no firm indication of the pH of these off-ridge springs we have argued that the solutions are likely to be alkaline rather than acid, We test the feasibility of this idea using EQ geochemical water-rock interaction modelling codes (Wolery 1983) and find that for a range of possible initial chemistries of Hadean seawater, the pH of issuing solutions at around 200 degrees C is around one or more units alkaline. Such pH values hold for interaction with both basaltic and komatiitic crust. The robustness of this result suggests to us that alkaline submarine springs of moderate temperature, carrying many hundreds of ppm HS to the ocean basins, are also serious contenders as sites for the origin of life, particularly as Hadean seawater was probably slightly acid, with a dissolved iron concentration approaching 100 ppm. On mixing of these solutions, supersaturation, especially of iron sulphide, would lead to the precipitation of colloidal gels. In our view iron sulphide was the likely substance of, or contributor to, the first vesicle membranes which led to life, as the supply organic molecules would have been limited in the Hadean. Such a membrane would have bid catalytic properties, expansivity, and would have maintained the natural chemiosmotic gradient, a consequence of the acid ocean and the alkaline interior to the vesicles.

Evolution, Planetary↗

Chemical evolution and the origin of life: bibliography supplement 1982.

The bibliography is the thirteenth annual supplement to the comprehensive bibliography on the same subject which was published in Space Life Sci. 2(1970), 225-295; 3(1972), 293-304; 4(1973), 309-329 and in Origins of Life 5(1974), 505-527; 6(1975), 285-300; 7(1976); 75-85; 8(1977), 59-66; 9(1978), 67-74; 10(1980), 69-87; 10(1980), 379-404; 11(1981), 273-288; 12(1982), 93-118; 13(1983), 61-80.

Earth, Planet↗

Carbon dioxide on the early earth.

This paper uses arguments of geochemical mass balance to arrive at an estimate of the partial pressure of carbon dioxide in the terrestrial atmosphere very early in earth history. It appears that this partial pressure could have been as large as 10 bars. This large estimate depends on two key considerations. First, volatiles were driven out of the interior of the earth during the course of earth accretion or very shortly thereafter. This early degassing was a consequence of rapid accretion,which gave the young earth a hot and rapidly convecting interior. Second, the early earth lacked extensive, stable continental platforms on which carbon could be stored in the form of carbonate minerals for geologically significant periods of time. In the absence of continental platforms on the early earth, the earth's carbon must have been either in the atmosphere or ocean or in the form of shortlived sedimentary deposits on ephemeral sea floor.

Atmosphere↗

An efficient lightning energy source on the early Earth.

Miller and Urey suggested in 1959 that lightning and corona on the early Earth could have been the most favorable sources of prebiotic synthesis. In 1991 Chyba and Sagan reviewed the presently prevailing data on electrical discharges on Earth and they raised questions as to whether the electrical sources of prebiotic synthesis were as favorable as was claimed. The proposal of the present paper is that localized lightning sources associated with Archaean volcanoes could have possessed considerable advantages for prebiotic synthesis over the previously suggested global sources.

Earth, Planet↗

Efficient near ultraviolet light induced formation of hydrogen by ferrous hydroxide.

The formation of hydrogen on irradiating ferrous ion in aqueous solution or suspension was studied over a wide range of pH. In addition to the known reaction in acid solution which decreases in yield with increasing pH and required far UV light, there is an efficient reaction occurring between pH 6 and 9 which utilizes near UV light. The latter reaction is an approximately linear function of both the concentration of ferrous ion and the light intensity. The quantum yield of hydrogen from the suspension of Fe(OH)2 at pH 7.2 is very high: > or = 0.3. The quantum yield decreases by a factor of five at 1 mole percent of ferric ions. To explain these observations it is proposed that an intermediate formed on excitation of the Fe(OH)2 polymer is further reduced by a neighboring Fe(+2) to form H2. These results support the work of Braterman et al. (1983) which claimed that the near UV driven photooxidation of ferrous ions could be responsible for formation of the Banded Iron Formations on the early earth. The efficient photoreaction observed in the present work could also serve as a source of active reducing equivalents to reduce CO2 and thus provide a solution to a dilemma in the arguments on the role of reduced carbon in the origin of life.

Carbon Dioxide↗

Multiple factors in the origin of the Cretaceous/Tertiary boundary: the role of environmental stress and Deccan Trap volcanism.

A review of the scenarios for the Cretaceous/ Tertiary (K/T) boundary event is presented and a coherent hypothesis for the origin of the event is formulated. Many scientists now accept that the event was caused by a meteorite impact at Chicxulub in the Yucatan Peninsula, Mexico. Our investigations show that the oceans were already stressed by the end of the Late Cretaceous as a result of the long-term drop in atmospheric CO2, the long-term drop in sea level and the frequent development of oceanic anoxia. Extinction of some marine species was already occurring several million years prior to the K/T boundary. The biota were therefore susceptible to change. The eruption of the Deccan Traps, which began at 66.2 Ma, coincides with the K/T boundary events. It erupted huge quantities of H2SO4, HCl, CO2, dust and soot into the atmosphere and led to a significant drop in sea level and marked changes in ocean temperature. The result was a major reduction in oceanic productivity and the creation of an almost dead ocean. The volcanism lasted almost 0.7 m.y. Extinction of biological species was graded and appeared to correlate with the main eruptive events. Elements such as Ir were incorporated into the volcanic ash, possibly on soot particles. This horizon accumulated under anoxic conditions in local depressions and became the marker horizon for the K/T boundary. An oxidation front penetrated this horizon leading to the redistribution of elements. The eruption of the Deccan Traps is the largest volcanic event since the Permian-Triassic event at 245 Ma. It followed a period of 36 m.y. in which the earth's magnetic field failed to reverse. Instabilities in the mantle are thought to be responsible for this eruption and therefore for the K/T event. We therefore believe that the K/T event can be explained in terms of the effects of the Deccan volcanism on an already stressed biosphere. The meteorite impact at Chicxulub took place after the onset of Deccan volcanism. It probably played a regional, rather than global, role in the K/T extinction.

Atmosphere↗

Hunting for Dark Matter particles with new detectors.

Although first hints of the existence of Dark Matter were observed by the Swiss astronomer Zwicky already in the 1930s, only in recent years has it become known that the universe, in fact, is dominated by particles whose nature is almost unknown and which have never been directly observed. Meanwhile, as the existence of these particles is postulated not only by astronomy, but also cosmology and theoretical particle physics, there is significant effort to detect them in a laboratory experiment and determine their physical properties. However, as the interaction rate between Dark Matter particles and ordinary matter is extremely low, detectors have to be extremely sensitive. Low temperature detectors have been available for more than a decade and have now reached the highest sensitivity for direct Dark Matter detection. In this article, we give a short overview of observational results that suggest the existence of Dark Matter particles and what physicists have learned so far about their properties. The main focus is on the experimental challenges and effort for their direct detection.

Astronomical Phenomena↗

Evolutionary events culminating in specific minerals becoming essential for life.

The environment in which living organisms evolved was apparently a primary determinant of which elements became essential for life. The first organic materials and, ultimately, life forms most likely were formed in an ancient sea containing minerals that provided structural integrity and catalytic ability to the first complex organic substances. The site at which life began has been suggested to be at the edge of the sea near sediments, or around a hydrothermal system. The strongest circumstantial evidence supports a hyperthermophilic beginning. Regardless of the site, the biological importance of elements tends to parallel oceanic abundance, but in higher forms of life this parallelism apparently has been mitigated by a natural selection process that resulted in some elements becoming more important because of their superior abilities over other elements to perform vital functions. The converse to biological importance is that toxicity of elements and oceanic abundance tends to be inversely related. The basis for this relationship may be that the efficiency of homeostatic mechanisms to cope with a high intake of a specific element probably reflects upon the exposure of an organism to the element during its evolution. Thus, a study of evolutionary events may be helpful in predicting and comprehending the essential and toxic nature of mineral elements in humans.

Adaptation, Biological↗

Evolution of antioxidant defence mechanisms.

The metabolic strengths, weaknesses, opportunities and threats of the metabolic ability to split water brought about a proliferation of biological systems, produced a toxic oxygenic environment, and were responsible for the development of antioxidant defence mechanisms. Evolution is driven by heritable adaptations which improve environmental 'fit'. Hence aerobic respiration, using oxygen as a nutrient, came to predominate in biological systems, and antioxidant defence mechanisms which prevent and neutralise toxic oxygen intermediates have become widespread, varied, coordinated and effective. Antioxidant defences are not infallible however. In humans, reactive oxygen species-induced damage is associated with the ageing process, and with chronic diseases including cancer and coronary heart disease. Interestingly, some important antioxidants, including ascorbic acid and the tocopherols, cannot be synthesised by humans and must be taken in the diet. Another antioxidant, uric acid, is found in much higher concentrations in humans than in other mammals, and levels are also affected by diet. In humans, therefore, antioxidant defence against toxic oxygen intermediates is species specific and heavily influenced by nutrition. In this article, the atmospheric and metabolic changes which produced both the threat and opportunity offered by an oxygenic environment are outlined. An overview of oxygen toxicity, and adaptations to oxidative stress in terms of evolution of antioxidant defences, is presented. Finally, suggested benefits underlying our curious inability to manufacture ascorbic acid, and the possible role of uric acid in human antioxidant defence, are briefly discussed with particular reference to nutrition and toxicology.

Adaptation, Biological↗

Early inner solar system impactors: physical properties of comet nuclei and dust particles revisited.

During the epoch of early bombardment, terrestrial planets have been heavily impacted by cometary nuclei and cometary dust particles progressively injected in the interplanetary medium. Stardust and Deep Impact missions confirm that the nuclei are porous, loosely consolidated objects, with densities below 1,000 kg m(-3), and that they often release small fragments of ices and dust. Recent numerical simulations of the light scattering properties of cometary dust particles indicate that they are highly porous, most likely fractal, and rich in absorbing organics compounds (with a mixture ratio of e.g. 33 to 60% in mass for comet Hale-Bopp). Taking into account the fact that porous structures survive more easily than compact ones during atmospheric entry, such results reinforce the scenario of the early terrestrial planets enrichment--in organics needed for life to originate--by comets.

Cosmic Dust↗

Mars primordial crust: unique sites for investigating proto-biologic properties.

The Martian meteorite collection suggests that intact outcrops or boulder-scale fragments of the 4.5 Ga Martian crust exist within tens of meters of the present day surface of Mars. Mars may be the only planet where such primordial crust samples, representing the first 100 Ma of a planet's environment, are available. The primordial crust has been destroyed on Earth by plate tectonics and other geological phenomena and is buried on the Moon under hundreds or thousands of meters of megaregoltih. Early Mars appears to have been remarkably similar to early Earth, and samples of rock from the first few Ma or first 100 Ma may reveal "missing link" proto-biological forms that could shed light on the transition from abiotic organic chemistry to living cells. Such organic snapshots of nascent life are unlikely to be found on Earth.

Earth, Planet↗

Tectonic control of the crustal organic carbon reservoir during the Precambrian.

Carbon isotopic trends indicate that the crustal reservoir of reduced, organic carbon increased during the Proterozoic, particularly during periods of widespread continental rifting and orogeny. No long-term trends are apparent in the concentration of organic carbon in shales, cherts and carbonates. The age distribution of 261 sample site localities sampled for well-preserved sedimentary rocks revealed a 500-700-Ma periodicity which coincided with tectonic cycles. It is assumed that the numbers of sites are a proxy for mass of sediments. A substantial increase in the number of sites in the late Archean correlates with the first appearance between 2.9 and 2.5 Ga of extensive continental platforms and their associated sedimentation. It is proposed that the size of the Proterozoic crustal organic carbon reservoir has been modulated by tectonic control of the volume of sediments deposited in environments favorable for the burial and preservation of organic matter. Stepwise increases in this reservoir would have caused the oxidation state of the Proterozoic environment to increase in a stepwise fashion.

Carbon↗