Primeval ocean

There is no doubt that in those times, all civilisations considered that there was a connection between natural events and their myths of the Earth s creation. Thus most of the Egyptians—whichever gods they worshipped—shared the common belief that the creation of the Earth could be compared with the appearance of a mound of land from the primeval ocean, just as every year they experienced the re-emergence of the land from the receding Nile floods. 

The second important source for the hydrosphere and the oceans are asteroids and comets. Estimating the amount of water which was brought to Earth from outer space is not easy. Until 20 years ago, it was believed that the only source of water for the hydrosphere was gas emission from volcanoes. The amount of water involved was, however, unknown (Rubey, 1964). First estimates of the enormous magnitude of the bombardment to which the Earth and the other planets were subjected caused researchers to look more closely at the comets and asteroids. New hypotheses on the possible sources of water in the hydrosphere now exist the astronomer A. H. Delsemme from the University of Toledo, Ohio, considers it likely that the primeval Earth was formed from material in a dust cloud containing anhydrous silicate. If this is correct, all the water in today s oceans must be of exogenic origin (Delsemme, 1992). 

What chemical composition can we assume for the ocean Unfortunately we have no clear results. Apart from the chemical components, it would be desirable to have information on temperature and pH values. We also do not know whether there was one single primeval ocean, or whether there were several. It is also possible that there were lakes and ponds with differing compositions. We must not forget that huge changes must have taken place on the primeval Earth s surface during the space of a few hundred million years. 

If the primeval atmosphere did not contain enough CO2 to maintain a greenhouse climate, the much lower solar irradiation at that time would have led to frozen oceans. But that would make almost all the assumed synthetic mechanisms for the formation of biomolecules impossible Bada et al. (1994) consider external help as a way out of this dilemma. They assume that the energy from meteor impacts (diameters up to around 100 km), converted into heat, would have sufficed to melt the oceanic ice. If such a process were to have occurred periodically, chemical evolution reactions (see Chap. 4) could have taken place in the ice-free periods and have led finally to biogenesis. 

We know nothing of the pH value of the primeval ocean. However, the acidic character of volcanic exhalations must have meant that the young ocean was also... 

According to Summers and Chang from NASA s Ames Research Center, Moffett Field (1993), the oxidation of Fe2+ to Fe3+ provided a possibility for the reduction of nitrites and nitrates to ammonia. This reaction would have been of great importance, as NH3 is required in many syntheses of biogenesis precursors. The authors assume that nitrogen was converted to NO in a non-reducing atmosphere, and thence to nitrous and nitric acids. These substances entered the primeval oceans in the form of acid rain , and here underwent reduction to NH3 with the help of Fe2+, thus raising the pH of the oceans to 7.3. Temperatures above 298 K favoured this reaction, which can be written as ... 

This success does, however, have a drawback the urea concentrations required could not possibly have existed in the primeval ocean. Thus, as in the case of other condensation reactions, one has to assume that there were ponds or lagoons, in which the necessary reagent concentrations could build up via evaporation of water. 

The same problem, the stability of the nucleobases, was taken up by Levi and Miller (1998). They wanted to show that a synthesis of these compounds at high temperatures is unrealistic, and thus they took a critical look at the high temperature biogenesis theories, such as the formation of biomolecules at hydrothermal vents (see Sect. 7.2). The half-life of adenine and guanine at 373 K is about a year, that of uracil about 12 years and of the labile cytosine only 19 days. Such temperatures could have easily been reached when planetoids impacted the primeval ocean. 

A more recent, extended study of purine synthesis via polymerisation of ammonium cyanide, described at the beginning of this section, showed that the yield of adenine from the non-hydrolyzed solution was only slightly temperature dependent. Shorter hydrolysis times for the insoluble polymerisation products led to higher adenine yields. When the solution is hydrolyzed at pH 8, the adenine yield is comparable to the value of 0.1% found for acidic hydrolysis (a model for the primeval ocean ). Increasing the hydrolysis time has no effect on the adenine yield because of its greater stability at pH 8. Hydrolysis of the black NH4CN polymer under acidic or neutral conditions results in an adenine yield of about 0.05% (Borquez et al., 2005). 

In all the experiments, the main decomposition products were phosphonates, which are also stable in concentrated solutions of Mg and Ca chlorides. In some experiments, pyrophosphate, and in smaller amounts triphosphate, could also be detected. The authors thus assume that the primeval ocean contained phosphonates as a source of phosphorus for reactions leading to biochemically relevant molecules. Iron meteorites could have delivered sufficient reduced phosphorus (Fe3P) to the primeval Earth, so the question of prebiotic phosphorus chemistry should be looked at in more detail in the future (Pasek and Lauretta, 2005). 

If prebiotic peptides and/or proteins were in fact initially formed in aqueous solution (the hypothesis of biogenesis in the primeval ocean ), the energy problems referred to above would have needed to be solved in order for peptide synthesis to occur. As discussed in Sect. 5.3, there is some initial experimental evidence indicating that the formation of peptide bonds in aqueous media is possible. An important criterion for the evolutionary development of biomolecules is their stability in the aqueous phase. The half-life of a peptide bond in pure water at room temperature is about seven years. The stability of the peptide bond towards cleavage by aggressive compounds was studied by Synge (1945). The following relative hydrolysis rates were determined experimentally, with the relative rate of hydrolysis for the dipeptide Gly-Gly set equal to unity ... 

In all simulation experiments carried out under assumed prebiotic conditions, the question of possible concentrations in a primeval ocean arises 0.1 M solutions appear unrealistic, as this would correspond to about 12 g of amino acid per litre of seawater Miller s lagoons and Darwin s ponds then come to mind, i.e., the concentration of dilute solutions in small localized areas due to evaporation of water. Recently, the attention of scientists has shifted towards concentration processes occurring at the surface of minerals however, many of the problems involved remain unsolved. 

In all cases, glycine oligomers were obtained, from the dimer up to the decamer yields were pressure dependent. The rate of polymerisation increased during the first 8 days and then remained constant until the 31st day. The authors conclude from their experimental results that abiotic polymerisation reactions during diagenesis were more likely to have occurred in deep-lying sediments than in the primeval ocean (Ohara et al 2007). 

However, the question must always be asked as to whether these processes could have taken place on the primordial Earth in its archaic state. The answer requires considerable fundamental consideration. Strictly speaking, most of the experiments carried out on prebiotic chemistry cannot be carried out under prebiotic conditions , since we do not know exactly what these were. In spite of the large amount of work done, physical parameters such as temperature, composition and pressure of the primeval atmosphere, extent and results of asteroid impacts, the nature of the Earth s surface, the state of the primeval ocean etc. have not so far been established or even extrapolated. It is not even sure that this will be possible in the future. In spite of these difficulties, attempts are being made to define and study the synthetic possibilities, on the basis of the assumed scenario on the primeval Earth. Thus, for example, in the case of the SPREAD process, we can assume that the surface at which the reactions occur could not have been an SH-containing thiosepharose, but a mineral structure of similar activity which could have carried out the necessary functions just as well. The separation of the copy of the matrix could have been driven by a periodic temperature change (e.g., diurnal variation). For his models, H. Kuhn has assumed that similar periodic processes are the driving force for some prebiotic reactions (see Sect. 8.3). 

In the same year, Miller and the biologist Antonio Lazcano (National Autonomous University of Mexico) spoke out against hypotheses that life could have originated at hydrothermal vents. They believe that the presence of thermophilic bacteria (the oldest life forms) does not prove that biogenesis occurred in the depths of the oceans. Stanley Miller sees a greater chance for successful pre-biotic chemistry under the conditions of a cold primeval Earth rather than at high temperatures in hydrothermal regions (Miller and Lazcano, 1995). 

The prebiotic primeval soup, i.e., the oft-cited mixture of organic molecules in the primordial ocean, or in ponds which could have arisen in many ways, e.g., in the atmosphere or the hydrosphere the substances concerned could also have been delivered from outer space. 

It is possible that colloidal photochemistry will provide a new approach to prebiotic syntheses. The work described previously on redox reactions at colloidal ZnS semiconductor particles has been carried on successfully by S. T. Martin and co-workers, who studied reduction of CO2 to formate under UV irradiation in the aqueous phase. ZnS acts as a photocatalyst in the presence of a sulphur hole scavenger oxidation of formate to CO2 occurs in the absence of a hole scavenger. The quantum efficiency for the formate synthesis is 10% at pH 6.3 acetate and propionate were also formed. The authors assume that the primeval ocean contained semiconducting particles, at the surface of which photochemical syntheses could take place (Zhang et al 2007). 

Pyrite is not only one of the key compounds in Wachtershauser s theory, but could also have fulfilled an important function for phosphate chemistry in prebiotic syntheses. A group in Rio de Janeiro studied the conditions for phosphate sorption and desorption under conditions which may have been present in the primeval ocean. In particular, the question arises as to the enrichment of free, soluble inorganic phosphate (Pi), which was probably present in low concentrations similar to those of today (10 7-10 8M) (Miller and Keffe, 1995). Experiments show that acid conditions favour sorption at FeS2, while a weakly alkaline milieu works in an opposite manner. Sorption of Pi can be favoured by various factors, such as hydrophobic coating of pyrite with molecules such as acetate, which could have been formed in the vicinity of hydrothermal systems, or the neutralisation of mineral surface charges by Na+ and K+. 

The processes occurring at hydrothermal systems in prebiotic periods were without doubt highly complex, as was the chemistry of such systems this is due to the different gradients, for example, of pH or temperature, present near hydrothermal vents. Studies of the behaviour of amino acids under simulated hydrothermal conditions showed that d- and L-alanine molecules were racemised at different rates the process was clearly concentration-dependent. L-Alanine showed a low enantiomeric excess (ee) over D-alanine at increasing alanine concentrations. The same effect was observed with metal ions such as Zn2+ in the amino acid solution. Thus, homochi-ral enrichment of biomolecules in the primeval ocean could have resulted under the conditions present in hydrothermal systems (Nemoto et al., 2005). 

The passage of the whole of the water in the oceans through hydrothermal systems (in about 10 million years), as discussed by Miller and Lazcano, is also not a convincing argument for a possible thermal destruction of all the biomolecules dissolved in the primeval ocean, as there could have been other smaller bodies of water on the primordial Earth which were not subject to such a passage. 

Were the first biomolecules formed in the primeval atmosphere or At hydrothermal vents in the depths of the primeval oceans or On the surface of the young Earth, at clay mineral surfaces or Via thioesters ... 

It is interesting that, when organic and inorganic tripolyphosphates were employed under the same conditions, only 0.2-0.6 % of the phosphate donor was utilized (Lowenstein, 1958, 1960 Tetas and Lowenstein, 1963 Le Port et al., 1971). Our experimental findings thus lead to the conclusion that, as the Earth cooled and a hydrosphere was formed on its surface, a variety of transphosphorylation reactions became possible in the primeval ocean, in particular, the phosphorylation of Pi by PolyP to give pyrophosphate. It should be noted that the non-enzymatic synthesis of PolyP and pyrophosphate on the primitive Earth could take place not only in solutions, but also on the surface of some minerals with anion-exchange properties (Arrhenius et al., 1993,1997). 

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