Where to Find Life? Not Europa

Now that we have found so many exoplanets, we might start to wonder whether they have life. It so happens I am going to give a presentation on this at a conference in about three weeks time, hence the temptation to focus attention on the topic. My argument is that whether a place could support life is irrelevant; the question is, could it get started? For the present, I am not considering panspermia, i.e. it came from somewhere else on the grounds that if it did, the necessities to reproduce still had to be present and if they were, life would probably evolve anyway. 

I consider the ability to reproduce to be critical because, from the chemistry point of view, it is the hardest to get right. One critical problem is reproduction itself is not enough; it is no use using all resources to make something that reproduces a brown sludge. It has to guess right, and the only way to do that is to make lots of guesses. The only way to do that is to tear to bits that which is a wrong guess and try again and re-use the bits. But then, when you get something useful that might eventually work, you have to keep the good bits. So reproduction and evolution have opposite requirements, but they have to go through the same entity. Reproduction requires the faithful transmission of information; evolution requires the information to change on transmission, but eventually not by much. Keep what is necessary, reject that which is bad. But how?

Information transfer requires a choice of entities to be attached to some polymer, and which can form specific links with either the same entity only (positive reproduction) or through a specific complementary entity (to make a negative copy). To be specific they have to have a strongly preferred attachment, but to separate them later, the attachment has to be able to be converted to near zero energy. This can be done with hydrogen bonds, because solvent water can make up the energy during separation. One hydrogen bond is insufficient; there are too many other things that could get in the road. Adenine forms two hydrogen bonds with uracil, guanine three with cytosine, and most importantly, guanine and uracil both have N-H bonds while adenine and cytosine have none; the wrong pairing either leads to a steric clash that pushes them apart or ends up with only one hydrogen bond that is not strong enough. Accordingly we have the condition for reliable information transfer. Further good news is these bases form themselves from ammonium cyanide, urea and cyanoacetylene, all of which are expected on an earth-like planet from my concept of planetary formation.

The next problem is to form two polymer strands that can separate in water. First, to link them something must have two links. For evolution to work, these have to be strong, but breakable under the right conditions. To separate, they need to have a solubilizing agent, which means an ionic bond. In turn, this means three functional valence electrons. Phosphate alone can do this. The next task is to link the phosphate to the bases that carries the information code. That something must also determine a fixed shape for the strands, and for this nature chose ribose. If we link adenine, ribose and phosphate at the 5 position of ribose we get adenosine monophosphate (AMP); if we do he same for uracil we get uridine monophosphate (UMP). If we put dilute solutions of AMP and UMP into vesicles (made by a long chain hydrocarbon-based surfactant) and let them lie on a flat rock in the sun and splash them from time to time with water, we end with what is effectively random “RNA” strands with over eighty units in a few hours. At this point, useful information is unlikely, but we are on the way.

Why ribose? Because the only laboratory synthesis of AMP from only the three constituents involves shining ultraviolet light on the mixture, and to me, this shows why ribose was chosen, even though ribose is one of the least likely sugars to be formed. As I see it, the reason is we have to form a phosphate ester specifically on the 5-hydroxyl. That means there has to be something unique about the 5-hydroxyl of ribose compared with all other sugar hydroxyl groups. To form such an ester, a hydroxyl has to hit the phosphate with an energy equivalent to the vibrations it would have at about 200 degrees C. Also, if any water is around at that temperature, it would immediately destroy the ester, so black smokers are out. The point about a furanose is it is a flexible molecule and when it receives energy (indirectly) from the UV light it will vibrate vigorously, and UV light has energy to spare for this task. Those vibrations will, from geometry, focus on the 5-hydroxyl. Ribose is the only sugar that has a reasonable amount of furanose; the rest are all in the rigid pyranose form. Now, an interesting point about ribose is that while it is usually only present in microscopic amounts in a non-specific sugar synthesis, it is much more common if the sugar synthesis occurs in the presence of soluble silica/silicic acid. That suggests life actually started at geothermal vents.

Now, back to evolution. RNA has a rather unique property amongst polymers in that the strands, when they get to a certain length and can be bent into a certain configuration and presumably held there with magnesium ions, they can catalyse the hydrolysis of other strands. It does that seemingly by first attacking the O2 of ribose, which breaks the polymer by hydrolysing the adjacent phosphate ester. The next interesting point is that if the RNA can form a double helix, the O2 is more protected. DNA is, of course, much better protected because it has no O2. So the RNA can build itself, and it can reorganise itself.

If the above is correct, then it places strong restrictions on where life can form. There will be no life in under-ice oceans on Europa (if they exist) for several reasons. First, Europa seemingly has no (or extremely small amounts of) nitrogen or carbon. In the very thin atmosphere of Europa (lower pressures than most vacuum pumps can get on Earth) the major gas is the hydroxyl radical, which is made by sunlight acting on ice. It is extremely reactive, which is why there is not much of it. There is 100,000 times less sodium it the atmosphere. Nitrogen was undetected. The next reason is the formation of the nucleic acid appears to require sunlight, and the ice will stop that. The next reason is that there is no geothermal activity that will make the surfactants, and no agitation to convert them to the vesicles needed to contain the condensation products, the ice effectively preventing that. There is no sign of hydrocarbon residues on the surface. Next, phosphates are essentially insoluble in water and would sink to the bottom of an ocean. (The phosphate for life in oceans on Earth tends to come from water washed down from erosion.) Finally, there is no obvious way to make ribose if there is no silicic acid to orient the formation of the sugar.

All of which suggests that life essentially requires an earth-like planet. To get the silicic acid you need geothermal activity, and that may mean you need felsic continents. Can you get silica deposits from volcanism/geothermal activity when the land is solely basalt? I don’t know, but if you cannot, this proposed mechanism makes it somewhat unlikely there was ever life on Mars because there would be no way to form nucleic acids.

Space News

There were two pieces of news relating to space recently. Thirty years ago we knew there were stars. Now we know there are exoplanets and over 4,000 of them have been found. Many of these are much larger than Jupiter, but that may be because the bigger they are, the easier it is to find them. There are a number of planets very close to small stars for the same reason. Around one giant planet there are claims for an exomoon, that is a satellite of a giant planet, and since the moon is about the size of Neptune, i.e.the Moon is a small giant in its own right, it too might have its satellite: an exomoonmoon. However, one piece of news is going to the other extreme: we are to be visited by an exocomet. Comet Borisov will pass by within 2 A.U. of Earth in December. It is travelling well over the escape velocity of the sun, so if you miss it in December, you miss it. This is of some interest to me because in my ebook “Planetary Formation and Biogenesis” I outlined the major means I believe were involved in the formation of our solar system, but also listed some that did not leave clear evidence in our system. One was exo-seeding, where something come in from space. As this comet will be the second “visitor” we have recorded recently, perhaps they are more common than I suspected.

What will we see? So far it is not clear because it is still too far away but it appears to be developing a coma. 2 A.U. is still not particularly close (twice the distance from the sun), so it may be difficult to see anyway, at least without a telescope. Since it is its first visit, we have no real idea how active it will be. It may be that comets become better for viewing after they have had a couple of closer encounters because from our space probes to comets in recent times it appears that most of the gas and dust that forms the tail comes from below the surface, through the equivalent of fumaroles. This comet may not have had time to form these. On the other hand, there may be a lot of relatively active material quite loosely bound to the surface. We shall have to wait and see.

The second piece of news was the discovery of water vapour in the atmosphere of K2-18b, a super-Earth that is orbiting an M3 class red dwarf that is a little under half the size of our sun. The planet is about eight times the mass of earth, and has about 2.7 times the radius. There is much speculation about whether this could mean life. If it has, with the additional gravity, it is unlikely that, if it did develop technology, it would be that interested in space exploration. So far, we know there is probably another planet in the system, but that is a star-burner. K2-18b orbits its star in 33 days, so birthdays would come round frequently, and it would receive about five per cent more solar radiation than Earth does, although coming from a red dwarf, there will be a higher fraction of infra-red light and less visible.

The determination of the water could be made because first, the star is reasonably bright so good signals can be received, second, the planet transits across the star, and third, the planet is not shrouded with clouds. What has to happen is that as the planet transits, electromagnetic radiation from the star is absorbed by any molecule at the frequency determined by the bond stretching or bending energies. The size of the planet compared with its mass is suggestive of a large atmosphere, i.e.it has probably retained some of the hydrogen and helium of the accretion disk. This conclusion does have risks because if it were primarily a water or ice world (water under sufficient pressure forms ice stable at quite high temperatures) then it would be expected to have an even greater size for the mass.

The signal was not strong, in part, from what I can make out, it was recorded in the overtone region of the water stretching frequency, which is of low intensity. Accordingly, it was not possible to look for other gases, but the hope is, when the James Webb telescope becomes available and we can look for signals in the primary thermal infrared spectrum, this planet will be a good candidate.So, what does this mean for the possibilities of life? At this stage, it is too early to tell. The mechanism for forming life as outlined in my ebook, “Planetary Formation and Biogenesis” suggests that the chances of forming life do not depend on planetary size, as long as there is sufficient size to maintain conditions suitable for life, such as an adequate atmospheric pressure, liquid water, and the right components, and it is expected that there will be an upper size, but we do not know what that will be, except again, water must be liquid at temperatures similar to ours. That would eliminate giants. However, more precise limits are more a matter of guess-work. The composition of the planet may be more important. It must be able to support fumaroles and I suspect it should have pre-separated felsic material so that it can rapidly form continents, with silica-rich water emitted, i.e.the type of water that forms silica terraces. That is because the silica acts as a template to make ribose. Ribose is important for biogenesis because something has to link the nucleobases to the phosphate chain. The nucleobases are required because they alone are the materials that form with the chemicals likely to be around, and they alone form multiple hydrogen bonds that can form selectively and add as a template for copying, which is necessary for retaining useful information. Phosphate is important because it alone has three functional sites – two to form a polymer, and one to convey solubility. Only the furanose form of the sugar seems to manage the linkage, at least under conditions likely to have been around at the time and ribose is the only sugar with significant amounts of the furanose form. I believe the absence of ribose means the absence of reproduction, which means the absence of life. But whether these necessary components are there is more difficult to answer.

Some Unanswered Questions from the Lunar Rocks

In the previous post I hinted that some of what we found from our study of moon rocks raises issues of self-consistency when viewed in terms of the standard paradigm. To summarize the relevant points of that paradigm, the argument goes that the dust in the accretion disk that was left behind after the star formed accreted into Mars-sized bodies that we shall call embryos, and these moved around in highly elliptical orbits and eventually collided to form planets. While these were all mixed up – simulations suggest what made Earth included bodies from outside Mars’ current orbit, and closer to the star than Mercury’s current orbit. These collisions were extraordinarily violent, and the Earth formed from a cloud of silicate vapours that condensed to a ball of boiling silicates at a little under 3000 degrees C. Metallic iron boils at 2862 degrees C, so it was effectively refluxing, and under these conditions it would extract elements such as tungsten and gold that dissolve in iron and take them with it to the core. About sixty million years after Earth formed, one remaining embryo struck Earth, a huge amount of silicates were sent into space, and the Moon condensed from this. The core of this embryo was supposedly iron, and it migrated into the Earth to join our core, leaving the Moon a ball of silicate vapour that had originated from Earth and condensed from something like 10,000 degrees C. You may now see a minor problem for Earth: if this iron took out all the gold, tungsten, etc, how come we can find it? One possibility is the metals formed chemical compounds. That is unlikely because at those temperatures elements that form only moderate-strength chemical bonds would not survive, and since gold is remarkably unreactive, that explanation won’t work. Another problem is that the Moon has very little water and no nitrogen. This easily explained through their being lost to space from the silicate vapours, but where did the Earth get its volatiles? And if the Moon did condense from such high temperatures, the last silicate to condense would be fayalite, but that was not included in the Apollo rocks, or if it were, nothing was made of that. This alone is not necessarily indicative, though, because fayalite is denser than the other olivines, and if there were liquid silicates for long enough it would presumably sink.

The standard paradigm invokes what is called “the late veneer”; after everything was over, Earth got bombarded with carbonaceous asteroids, which contain water, nitrogen, and some of these otherwise awkward metals. It is now that we enter one of the less endearing aspects of modern science: everything tends to be compartmentalised, and the little sub-disciplines all adhere to the paradigm and add small findings that support their view, even if they do not do so particularly well, and there is a reluctance to look at the overall picture. The net result is that while many of the findings can be made to seemingly provide answers to their isolated problems, there is an overall problem with self-consistency. Further, clues that the fundamental proposition might be wrong are carefully shelved.

The first problem was noted at the beginning of the century: the isotope ratios of metals like osmium from such chondrites are different from our osmium. There are various hand-waving argument to the extent that it could just manage if it were mixed with enough of our mantle, but leaving whether the maths are right aside, nobody seems to have noticed the only reason we are postulating this late veneer is that originally the iron stripped all the osmium from the mantle. You cannot dilute A with B if B is not there. There are a number of other reasons, one of which is the nitrogen of such chondrites has more 15N than our nitrogen. Another is to get the amounts of material here we need a huge amount of carbonaceous asteroids, but they have to come through the ordinary asteroids without perturbing them. That takes some believing.

But there is worse. All the rocks found by the Apollo program have none of the required materials and none of the asteroidal isotope signatures. The argument seems to be, they “bounced off” the Moon. But the Moon also has some fairly ferocious craters, so why did the impactors that caused them not bounce off? Let’s suppose they did bounce off, but they did not bounce off the Earth (because the only reason we argue for this is that we need them, so it is said, to account for our supply of certain metals). Now the isotope ratios of the oxygen atoms on the Moon have a value, and that value is constant over rocks that come from deep within the Moon, thanks to volcanism, and for the rocks from the highlands, so that is a lunar value. How can that be the same as Earth’s if Earth subsequently got heavily bombarded with asteroids that we know have different values? My answer, in my ebook “Planetary Formation and Biogenesis” is simple: there were no embryo impacts in forming Earth therefore the iron vapours did not extract out the heavy elements, and there were no significant number asteroid impacts. Almost everything came here when Earth accreted, and while there have been impacts, they made a trivial contribution to Earth’s supply of matter.

Where are the Planets that Might Host Life?

In the previous posts I showed why RNA was necessary for primitive life to reproduce, but the question then is, what sort of planets will have the necessary materials? For the rocky planets, once they reached a certain size they would attract gas gravitationally, but this would be lost after the accretion disk was removed by the extreme UV put out by the new star. Therefore all atmosphere and surface water would be emitted volcanically. (Again, for the purposes of discussion, volcanic emission includes all geothermal emissions, e.g. from fumaroles.) Gas could be adsorbed on dust as it was accreted, but if it were, because heats of adsorption of the gases other than water are very similar, the amount of nitrogen would roughly equal the amount of neon. It doesn’t. (Neon is approximately at the same level as nitrogen in interstellar gas.)

The standard explanation is that since the volatiles could not have been accreted, they were delivered by something else. The candidates: comets and carbonaceous asteroids. Comets are eliminated because their water contains more deuterium than Earth’s water, and if they were the source, there would be twenty thousand times more argon. Oops. Asteroids can also be eliminated. At the beginning of this century it was shown that various isotope ratios of these bodies meant they could not be a significant source. In desperation, it was argued they could, just, if they got subducted through plate tectonics and hence were mixed in the interior. The problem here is that neither the Moon nor Mars have subduction, and there is no sign of these objects there. Also, we find that the planets have different atmospheres. Thus compared to Earth, Venus has 50% more carbon dioxide (if you count what is buried as limestone on Earth), four times more nitrogen, and essentially no water, while Mars has far less volatiles, possibly the same ratio of carbon dioxide and water but it has far too little nitrogen. How do you get the different ratios if they all came from the same source? It is reasonably obvious that no single agent can deliver such a mix, but since it is not obvious what else could have led to this result, people stick with asteroids.

There is a reasonably obvious alternative, and I have discussed the giants, and why there can be no life under-ice on Europa https://wordpress.com/post/ianmillerblog.wordpress.com/855) and reinforced by requirement to join ribose to phosphate. The only mechanism produced so far involves the purine absorbing a photon, and the ribose transmitting the effect. Only furanose sugars work, and ribose is the only sugar with significant furanose form in aqueous solution. There is not sufficient light under the ice. There are other problems for Europa. Ribose is a rather difficult sugar to make, and the only mechanism that could reasonably occur naturally is in the presence of soluble silicic acid. This requires high-temperature water, and really only occurs around fumaroles or other geothermal sites. (The terrace formations are the silica once it comes out of solution on cooling.)

So, where will we find suitable planets? Assuming the model is correct, we definitely need the dust in the accretion disk to get hot enough to form carbides, nitrides, and silicates capable of binding water. Each of those form at about 1500 degrees C, and iron melts at a bit over this temperature, but it can be lower with impurities, thus grey cast is listed as possible at 1127 degrees C. More interesting, and more complicated, are the silicates. The calcium aluminosilicates have a variety of phases that should separate from other silicate phases. They are brittle and can be easily converted to dust in collisions, but their main feature is they absorb water from the gas stream and form cements. If aggregation starts with a rich calcium aluminosilicate and there is plenty of it, it will phase separate out and by cementing other rocks and thus form a planet with plenty of water and granitic material that floats to the surface. Under this scene, Earth is optimal. The problem then is to get this system in the habitable zone, and unfortunately, while both the temperatures of the accretion disk and the habitable zone depend on the mass of the star, they appear to depend on different functions. The net result is the more common red dwarfs have their initial high-temperature zone too close to the star, and the most likely place to look for life are the G- and heavy K-type stars. The function for the accretion disk temperature depends on the rate of stellar accretion, which is unknown for mature stars but is known to vary significantly for stars of the same mass, thus LkCa 15b is three times further away than Jupiter from an equivalent mass star. Further, the star must get rid of its accretion disk very early or the planets get too big. So while the type of star can be identified, the probability of life is still low.

How about Mars? Mars would have been marginal. The current supply of nitrogen, including what would be lost to space, is so low life could not emerge, but equally there may be a lot of nitrogen in the solid state buried under the surface. We do not know if we can make silicic acid from basalt under geochemical conditions and while there are no granitic/felsic continents there, there are extrusions of plagioclase, which might do. My guess is the intermittent periods of fluid flow would have been too short anyway, but it is possible there are chemical fossils there of what the path towards life actually looked like. For me, they would be of more interest than life itself.

To summarise what I have proposed:

  • Planets have compositions dependent on where they form
  • In turn, this depends on the temperatures reached in the accretion disk
  • Chemicals required for reproduction formed at greater than 1200 degrees C in the accretion disk, and possibly greater than 1400 degrees C
  • Nucleic acids can only form, as far as we know, through light
  • Accordingly, we need planets with reduced nitrogen, geothermal processing, and probably felsic/granitic continents that end in the habitable zone.
  • The most probable place is around near-earth-sized planets around a G or heavy K type star
  • Of those stars, only a modest proportion will have planets small enough

Thus life-bearing planets around single stars are likely to be well-separated. Double stars remain unknown quantities regarding planets. This series has given only a very slight look at the issues. For more details, my ebook Planetary Formation and Biogenesis(http://www.amazon.com/dp/B007T0QE6I) has far more details.

Why Life Must Start with RNA and not Something Else.

In the previous post, I argued that reproduction had to start with RNA, but that leaves the obvious question, why not something else? The use of purines and pyrimidines to transfer energy arises simply because the purines and pyrimidines are the easiest to form, given the earliest atmosphere almost certainly was rich in ammonia, hydrogen cyanide, cyanocetylene, and urea would soon be formed. Some may argue with the “easily formed”, however leaving a sample of ammonium cyanide and urea to its own devices will get nucleobases. Cytosine is a little more difficult, but with available cyanoacetylene, it is reasonably likely. The important point is that if you accept my mechanism for how rocky planets form, these chemicals are going to be prolific. I shall justify that later. The important thing about these chemicals is that they lead to the formation of multiple hydrogen bonds only with their partners. As explained in the last post, there is no alternative to hydrogen bonds for transferring information, and these are the only chemicals that can provide accuracy under abiogenic conditions.

The polymer linking agent is phosphate, so why phosphate? Phosphoric acid has three hydrogen atoms that are available for substitution, i.e.it can form three functions. Two are to form esters and as I noted previously, the third is to provide solubility. The solubility is important because if there was not anionic repulsion, the strands would bundle together and reproduction would not work. The strands would also not provide catalysis, which occurs because a strand can fold around a cation like magnesium and form the shapes that seem to be needed. The good news is that unlike in enzymes, it can rearrange the magnesium and thus get different effects. Of course, enzymes are hugely more effective, but an enzyme generally only does one thing.

The polymer forms esters by phosphate bonding to a sugar. Think of the reaction as

P – OH  + HO – C    ->  P – O – C  + H2O       (1)

where P is the phosphorus of a phosphate or phosphoric acid, and C is the carbon atom of a sugar. Note that this reaction is reversible, but at room temperature the bonds are quite stable. These ester bonds are very strong, which is important because you do not want your carefully prepared polymer to randomly fall to bits. On the other hand, it must be able to be disrupted or substituted and not be essentially fixed, as would happen if proteins were used for information transfer. The reason is, life is evolving by random trials, and it is important that since many of these trials will be unproductive, there has to be a way to recover an many of the valuable chemicals as possible for further trials, and also to unclutter the system so that something that conveys advantages does not get lost in the morass of failures or otherwise useless stuff. Only phosphate offers these properties. In principle, you might argue for arsenate, but its bonds are weaker, thus less reliable, and worse, arsenic reacts with hydrogen sulphide (common around fumaroles which as we shall see are necessary sites) to form insoluble sulphides. These are the very pretty yellow layers in geothermal areas. No other element will do.

There are a variety of other sugars that if used to link nucleobases to phosphate will form duplexes, so the question then is, why weren’t they used? The ability to catalyse its own scission is the first of two reasons why ribose is so important. Once the strands get long enough to fold around themselves, catalysis starts, and one of the possible catalytic reactions is the promotion of the remaining OH group on the ribose to help water send the reaction (1) into reverse, which would break a link in the polymer chain. Deoxyribose does not have such a free hydroxyl and hence does not have this option, which is why DNA ended up being the information transfer chemical once a life form that had something worth keeping had emerged. What this means is that RNA has the opportunity to mutate, which is a big help in getting evolution going, and when it is broken, the bits remain available for further tries in some rearranged form.

The question then is, how do you form the phosphate ester? You mix phosphate and the sugar in solution and – oops, nothing happens. Reaction (1) is so slow at ambient temperature that you could sit there indefinitely, however, if you heat it, it does proceed. However, the rate of a reaction like this depends on the product of the concentrations on each side, with such a product on the right-hand side determining the rate of the reaction going from right to left. If you look at (1), it probably occurs to you that in aqueous solution, the concentration of water is far greater than the concentration of sugar. You will see people say that life could start around black smokers, but when you check, at the temperatures they require for the forward reaction to go it requires the concentration of water to be less than about 2%. Good luck getting that at the bottom of the ocean. You may protest that nevertheless there is life there, devouring emerging nutrients. True, although the ocean acts as a cooling bath, and the life forms have evolved protective systems. There are no such things when life is getting started. Life has moved to be close to black smokers but it did not start there.

What we need is a more precise way of delivering the required energy to the reaction site. So far, one and only one method has been found to make such initial linkages, and that is photochemical. If adenine is irradiated with light in the presence of ribose and phosphate, you get AMP, and even ATP. We now see why only ribose was chosen. AMP, and for that matter, RNA, link the nucleobases and phosphate through the ribofuranose form. Such sugars can exist in two forms: a furanose (a five-membered ring involving an oxygen atom linked to C1 of the sugar) and a pyranose form (the six-membered equivalent.). Now the first important point about a sugar is it cannot transmit electronic effects arising from the nucleobase absorbing a photon. However, it can transmit mechanical vibrational energy, and this is where the furanose becomes important. While the pyranose form is always rigid, the furanose form is flexible. The reason ribofuranose can form the links, in my opinion, is it can transmit and focus the mechanical energy to the free C-5 which will vibrate vigorously like the end of a whip and form the phosphate ester. Ribose is important because it is the only sugar with a reasonable amount of furanose form in aqueous solution. It is also worth noting that in the original experiments, no phosphate ester was formed from the pyranose form. As the furanose is used, the equilibrium ensures pyranose maintains the furanose/pyranose ratio.

That leaves open the question, how are the polymers formed? It appears that provided you can get the mers embedded in a lipid micelle or vesicle (the most primitive form of the cell wall), leaving these in the sun on a hot rock to dry them out leads to polymers of about 80 units in an hour. This is the first reason why life probably started around geothermal vents on land. Plenty of hot rocks around, with water splashes to replenish the supply of mers, and sunlight to form them. The second reason will be in the following post.

The title statement can now be answered. Life must start with RNA because it is the only agent that can lead to biological reproduction without external assistance. I started the last post indicating I would show what sort of planets might harbour life. The series is nearly there, but some might like to try the last step for themselves.

What do we need for life?

One question that intrigues man people is, is there life in the Universe besides what we see? Logic would say, almost certainly yes. The reason is we know there is a non-zero probability that it can form elswhere because it did here. That probability may be small but there is an enormous number of stars in the Universe (something in excess of 10^22 that we can see) that the conditions that led to life here must be reproduced a very large number of times. Of course, while there are such a large number of stars, by far the most are at such an extraordinarily large distance from us that they are essentially irrelevant. For the bulk of them, it took the light more than ten billion years to get here. But if we were to look for life nearby, where would we look? To answer that, we need to ask ourselves, what conditions are needed to get life started? The issue is NOT where can life exist, but rather where can it form. We know life can be found now on Earth in a wide range of environments, but that does not mean it can form there. It can migrate from somewhere else, gradually evolving systems needed to stabilize it to the new environment. The most obvious example is life emerging from the water to live on land. Nobody suggests life did not start in water because you need a solution to move nutrients around.

The first question to ask is, what are the most difficult things to achieve for life to get started? I think the four hardest things to get started are reproduction, energy transport, solubilization, and catalysis. Catalysis is required to make the chemical reactions that are desirable to go faster, and thus get more of the available resources going in the desired direction. (In this, when I use the word “desired” I mean to get on a right track to where life can get going and then support that choice during subsequent evolution. I do not mean to imply some sort of planning or directing.) Solubilization is required because many of the chemicals with functions that will be needed are not soluble in water, and hence they would simply settle out as a layer of brown gunk, which, as an aside, is what happens in many experiments designed to simulate the origin of life. What needs to happen is that something joins on at a place that does not spoil the function and then conveys solubility. Energy transport is a critical problem: if you do not have something that stores energy, functionality is restricted to microdistances from energy inputs.

Each of these critical functions, as well as reproduction, as I shall show below, depend on forming phosphate esters. Thus energy transport is mediated by adenosine tripolyphosphate (ATP), solubilisation of many of the most primitive cofactors that do not contain a lot of nitrogen or hydroxyl groups is aided by an attached adenosine monophosphate (AMP), initial catalysts came from ribozymes, RNA would be the initial source of reproduction, and both ribozymes and RNA (the latter is effectively just far longer strands of the former) are both constructed of AMP or the equivalent with different nucleobases. The commonality is the ribose and phosphate ester.

Catalysis is an interesting problem. Currently, enzymes are used, but life could not have started that way. The reason lies in the complexity of enzymes. The enzyme that will digest other protein, and hence make chemicals available from failed attempts at guessing the structure of a useful enzyme, has a precise sequence of three hundred and fifteen amino acids. There are twenty different common amino acids used (and in abiogenic situations, a lot more available) and these occur in D- and L- configurations, except for glycine, which means the probability of getting this enzyme is two in 39^315. That number is incredibly improbable. It makes selecting a specific proton in the entire Universe trivial in comparison. Worse, that catalyses ONE reaction only. That is not how initial catalysis happened.

Now, look at the problem of reproduction. Once a polymer is formed that can generate some of whatever requirements life needs, if it cannot copy itself, then it is a one-off wonder, and eventually it will degrade and be lost without a trace. Reproduction involves the need to transfer information, which in this case is some sort of a pattern. The problem here is the transfer must be accurate, but not too accurate initially, and we need different entities. By that I mean, if you just reproduced the same entity, such as in polyethene, you have two units of information: what it is and how long it is, but that second one is rather useless because life has no way of measuring the length without having a very large set of reference molecules. What life here chose appears to have been RNA, at least to start with. RNA has two purines and two pyrimidines, and it pairs them in a double helix. When reproduction occurs, one strand is the negative of the other, but if the negative pairs, we now have two strands that are equivalent to each original strand. (you retain the original.) There are four variations possible from the canonical units at any given position, and once you have many millions of units, a lot of information can be coded.

Why ribonucleic acid? The requirement is to be able to transfer information reliably, but not too accurately (I shall explain why not in a later post.) To do that, the polymer strands have to bind, and this occurs through what we call hydrogen bonds, which each give a binding energy of about 13 kJ/mol. These are chosen because they are weak enough to be ruptured, but strong enough you can get preferences. Thus adenine binds with uracil through two hydrogen bonds, which generates a little over 26 kJ/mol. (For comparison, a carbon-carbon bond is about 360 kJ/mol.) To get the 26 kJ/mol. the two hydrogen bonds have to be formed, and that can only happen of the entities have the right groups in the correct rigid configuration. When guanine bonds with cytosine, three such hydrogen bonds are formed, and the attraction is just under 40 kJ/mol. Guanine can also bind with uracil generating 26 kJ/mol., so information transfer is not necessarily totally accurate.

This binding through hydrogen bonds is critical. The bonding is strong enough to give a significant preference for each mer, but once the polymer gets long enough, the total energy (the sum of the energy of the individual pairs) holding the strands together gets to be those energies above multiplied by the number of pairs. If you have a million pairs, the strength of diamond becomes trivial, yet to reproduce, the strands must be separated. Hydrogen bonds can be separated because as the strands start to separate, water also hydrogen bonds and thus makes up for the linking energy. However, that alone is insufficient because the strand itself would be insoluble in water, and if so, the two strands linked together would remain insoluble (for those who know what this means, entropy strongly favours keeping the strands together). To achieve this, we need something that joins the mers into a chain, adds solubility, forms stable chemical bonds in general but is equally capable of being broken so that if the information creates something that is useless, we can recycle the chemicals. Only phosphate fills these requirements, but phosphate does not bind nucleobases together. Something intermediate is required, and that something is ribose.

In the next posts on this topic, I shall show you where this leads in seeing where life might be.

Rocky Planets and their Atmospheres

The previous post outlined how I consider the rocky planets formed. The most important point was that Earth formed a little inside the zone where calcium aluminosilicates could melt and phase separate while the star was accreting, as when the disk cooled down this would create a dust that, when reacted with the water vapour in the disk, would act as a cement. The concept is that this would bind basaltic rocks together, especially if the dust was formed in the collision between the rocks. The collisions were, by and large, gentle at first, driven by the gas sweeping smaller material closer to bigger material. Within this proposed mechanism, because the planet grows by collisions with objects at low relative velocities, the planet starts with a rather porous structure. It gradually heats up due to gravitational potential energy being converted to heat as more material lands, and eventually, if it gets to 1550 degrees, iron melts and runs down the pores towards the centre, while aluminosilicates, with densities about 0.4 – 1.2 g/cm3less than basalt, move upwards. The water is driven from the cements and also rises through the porous rock to eventually form the sea. The aluminosilicates form the granitic/felsic continents upon which we live.

Earth had the best setting of aluminosilicates because after the accretion disk cooled, it was at a temperature where these absorbed water best. Venus is smaller because it was harder to get started, as the cement was sufficiently warm that water had trouble reacting, but once it got going the density of basaltic and iron-bearing rocks was greater. This predicts Venus will have small granitic/felsic cratons on its surface; we have yet to find them. Mercury probably formed simply by accreting silicates and iron during the stellar accretion stage. Mars did not have a good supply of separated aluminium oxides, so it is very short of granite/felsic rock, although the surface of Syrtis Major appears to have a thin sheet of plagioclase. Because the iron did not melt at Mars, its outer rock would have contained a lot of iron dust or iron oxide. Reaction with water would have oxidised it subsequently. Most Martian rocks have roughly the same levels of calcium as Earth, about half the aluminium content, and about half as much again of iron oxide, which as an aside, may be why Mars does not have plate tectonics: because of the iron levels it cannot make eclogite which is necessary for pull subduction.

However, there is also a lot of chemistry going on in the stage 1 accretion disk in addition to what I have used to make the planets. In the vapour phase, carbon is mainly in the form of carbon monoxide in the rocky planet zone, but this can react catalytically with hydrogen to make methanol and hydrocarbons. These will have a very short lifetime and would be what chemists call reactive intermediates, but they would condense on silicates to make carbonaceous material, and they will react with oxides and metal vapour to make carbides. At the temperatures of at least the inner rocky planet zone, nitrogen reacts with oxides to make nitrides, and with carbides to make cyanamides, and some other materials.

Returning to the planet while it is heating up, the water coming off the cement should be quite reactive. If it meets iron dust it will oxidise it. If it meets a carbide there will be options, although the metal will invariably become an oxide. If the carbide was of the structure of calcium carbide it will make acetylene. If it oxidises anything, it will make hydrogen and the oxide. For many carbides it may make methane and metal oxide, or carbon monoxide, and invariably some hydrogen. Carbon monoxide can be oxidised by water to carbon dioxide, making more hydrogen, but carbon monoxide and hydrogen make synthesis gas, and a considerable variety of chemicals can be made, most of which are obvious contenders to help make life. Nitrides react with water largely to make ammonia, but ammonia is also reactive, and hydrogen cyanide and cyanoacetylene should be made. In the very early stages of biogenesis, hydrogen cyanide is an essential material, even though now it is poisonous.

This explains a little more of what we see in terms of the per centage composition. Mars, as noted above, has extremely little felsic/granitic material, and has a much higher proportion of iron oxide. It has less carbon dioxide than expected, even after allowing for some having escaped to space, and that is because since Mars was cooler, the high temperature carbide formation was slower. It has less water because the calcium silicates absorb less, although there is an issue here of how much is buried under the surface. The nitrogen is a puzzle. Mars has extremely little nitrogen, and the question is, why not. One possibility is that the temperatures were too low for significant nitride production. The other possibility, which I proposed in my novel Red Gold, is that at least some nitrogen was there and was emitted as ammonia. If so, it solves another puzzle: Mars has clear signs of ancient river flows, but all evidence is it was too cold for ice to melt. However, ammonia dissolves in ice and melts it down to minus eighty degrees Centigrade. So, in my opinion, the river flows were ammonia/water solutions. The carbon would have been emitted as methane, but that oxidises to carbon dioxide in the presence of water vapour and UV light.  Ammonia reacts with carbon dioxide first to form ammonium carbonate (which will also lower the melting point of ice) then urea. If I am right, there will be buried deposits of urea, or whatever it converts to after billions of years, in selected places on Mars.

The experts argue that methane and ammonia would only survive for a few years due to the UV radiation. However, smog would tend to protect them, and Titan still has methane. Liquid water also tends to protect ammonia. There are two samples from early Earth. One is of the atmosphere encased in rock at Isua, Greenland. It contains methane (as well as some hydrogen). The other is from Barberton (South Africa) which contains samples of seawater trapped in rock. The concentration of ammonia in seawater at 3.2 Gy BP was such that about 10% of the planet’s nitrogen currently in the atmosphere was in the sea in the form of ammonia.

We finally get to the initial question: why is Venus so different? The answer is simple. It will have had a lower per centage of cement and a high per centage of basalt simply because it formed at a hotter place. Accordingly, it would have much less water than Earth. However, it would have had more carbides and nitrides, and that valuable water got used up making the atmosphere, and in oxidising sulphur to sulphates. Accordingly, I expect Venus to have relatively small deposits of granite on the surface.

There is also the question of the deuterium to hydrogen ratio, which is at least a hundred times higher than solar. If the above mechanism is right, all the oxygen in the oxides, and all the nitrogen in the atmosphere, came from water reacting. My answer is that just about all the water was used up making the atmosphere, sulphates, and whatever. The initial reaction is of the sort:

R – X  + H2O  ->  R –OH + H – X

In this, one hydrogen atom has to transfer from the water to the X (where it will later be dislodged and lost to space). If there is a choice, the atom that is most weakly bonded will move, and deuterium is bonded quite more strongly than hydrogen. The electronic binding is the same, but there are zero point vibrations, and hydrogen, being lighter uses more of this as vibrational energy. In general chemistry, the chemical isotope effect, as it is called, can make the hydrogen between four and twenty-five times more likely to move, depending on the activation energy. Venus did not need to lose the supply of water equivalent to Earth’s oceans to get its high deuterium content; the chemical isotope effect is far more effective.

Further details can be found in my ebook “Planetary Formation and Biogenesis”http://www.amazon.com/dp/B007T0QE6I.