Did Mars Have an Ocean?

It is now generally recognized that Mars has had fluid flows, and a number of riverbeds, lake beds, etc have been identified, but there are also maps on the web of a proposed Northern Ocean. It has also been proposed that there has been polar wander, and this Northern Ocean was more an equatorial one when it was there about 3.6 billion years ago. The following is a partial summary from my ebook “Planetary Formation and Biogenesis”, where references to scientific papers citing the information can be found.

Various options include: (with bracketed volumes of water in cubic kilometre): a northern lake (54,000), the Utopia basin, (if interconnected, each with 1,000,000), filled to a possibly identified ‘shoreline’ (14,000,000), to a massive northern hemisphere ocean (96,000,000). Of particular interest is that the massive channels (apart from two that run into Hellas) all terminate within an elevation of 60 m of this putative shoreline.

A Northern Ocean would seem to require an average temperature greater than 273 degrees K, but the faint sun (the sun is slowly heating and three and a half billion years ago, when it is assumed water flowed, it had only about two thirds its current output) and an atmosphere restricted to CO₂/H₂O leads in most simulations to mean global temperatures of approximately 225 degrees K. There is the possibility of local variations, however, and one calculation claimed that if global temperatures were thirty degrees higher, local conditions could permit Hellas to pond if the subsurface contained sufficient water, and with sufficient water, the northern ocean would be possible and for maybe a few hundred years be ice free. A different model based on simulations, assuming a 1 bar CO₂ atmosphere with a further 0.1 bar of hydrogen, considered that a northern ocean would be stable up to about three billion years. There is quite an industry of such calculations and it is hard to make out how valid they are, but this one seems not to be appropriate. If we had one bar pressure of carbon dioxide for such a long time there would be massive carbonate deposits, such as lime, or iron carbonates, and these are not found in the required volumes. Also, the gravity of Earth is insufficient to hold that amount of hydrogen and Mars has only 40% of Earth’s gravity. This cannot be correct.

This northern ocean has been criticized on the basis that the shoreline itself is not at a constant gravitational potential, and variations of as much as 1.8 km in altitude are found. This should falsify the concept, except that because this proposed ocean is close to the Tharsis volcanic area, the deformation of forming these massive volcanoes could account for the differences. The magma that is ejected had to come from somewhere, and where it migrated from would lead to an overall lowering of the surface there, while where it migrated to would rise.

Support for a northern sea comes from the Acidalia region, where resurfacing appears to have occurred in pulses, finishing somewhere around 3.65 Gy BP.  Accumulation of bright material from subsequent impacts and flow-like mantling was consistent with a water/mud northern ocean. If water flows through rock to end in a sea, certain water-soluble elements are concentrated in the sea, and gamma ray spectra indicates that this northern ocean is consistent with enhanced levels of potassium and possibly thorium and iron. There may, however, be other reasons for this. While none of this is conclusive, a problem with such data is that we only see the top few centimeters and better evidence could be buried in dust.

Further possible support comes from the Zhurong rover that landed in Utopia Planitia (Liu, Y., and 11 others. 2022. Zhurong reveals recent aqueous activities in Utopia Planitia, Mars. Science Adv., 8: eabn8555). Duricrusts formed cliffs perched through loose soil, which requires a substantial amount of water, and also avoids the “buried in dust” problem. The authors considered these were formed through regolith undergoing cementation through rising or infiltration of briny groundwater. The salt cements precipitate from groundwater in a zone where active evaporation and accumulation can occur. Further, it is suggested thus has occurred relatively recently. On the other hand, ground water seepage might also do it, although the water has to be salty.

All of which is interesting, but the question remains: why was the water liquid? 225 degrees K is about fifty degrees below water’s freezing point. Second, because the sun has been putting out more heat, why is the water not flowing now? Or, alternatively, as generally believed, why did it flow for a brief period than stop? My answer, somewhat unsurprisingly since I am a chemist, is that it depends on chemistry. The gases had to be emitted from below the surface, such as from volcanoes or fumaroles. The gases could not have been adsorbed there as the planet accreted otherwise there would be comparable amounts of neon as to nitrogen on the rocky planets, and there is not. That implies the gases were accreted as chemical compounds; neon was not because it has no chemistry. When the accreted compounds are broken down with water, ammonia forms. Ammonia dissolves very rapidly in water, or ice, and liquefies it down to about 195 degrees K, which is well within the proposed range stated above. However, ammonia is decomposed slowly by sunlight, to form nitrogen, but it will be protected when dissolved in water. The one sample of seawater from about 3.2 billion years ago is consistent with Earth having about 10% of its nitrogen still as ammonia. However, on Mars ammonia would slowly react with carbon dioxide being formed, and end up as solids buried under the dust.

Does this help a northers sea? If this is correct, there should be substantial deposits of nitrogen rich solids below the dust. If we went there to dig, we would find out.

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Reducing Electricity Usage in Your Refrigerator

When thinking about battling climate change, did you know that a major electricity consumer in your house is your refrigerator? The International Institute of Refrigeration (yes, there are institutes for just about everything) estimates that about 20% of all electricity used is expended on vapour compression refrigeration. The refrigerator works by compressing a vapour, often some sort of freon, or in industry, with ammonia, and when compressed it gives off heat. When you ship it somewhere else and expand it, the somewhere else gets colder. This is also the principle of the heat pump and various air conditioning units. Compress gas here to add heat from a heat exchanger; ship the gas there and expand it, where it cools a heat exchanger. The compression and expansion of gas moves heat from A to B, hence the name heat pump. Also, the refrigerant gases tend to be powerful greenhouse gases. One kilogram of R410a has the same greenhouse impact as two tonne of carbon dioxide. Refrigerants leak into the atmosphere from faulty equipment or when equipment is not properly disposed of.

It is possible to heat or cool without any gas through the Peltier effect. Basically, when electric current passes between two conductors, heating or cooling effects may be generated. There are commercial solid-state such cooling systems, but they suffer from high cost and poor efficiency, in part because the effect is restricted to the specific junction.

There is an alternative. Some solid state materials can cool when they are subjected to strain, which is generated from an external field, such as  the electric or magnetic fields, or simply pressure. So far most efforts have been focused on the magnetic field, and one material, Mn3SnC apparently gives significant cooling,  but the magnetic field has to be greater than 2 tesla. That means expensive and bulky magnets, and additionally the refrigerator, if it used them, would have to be a “no-go” area for credit cards, and possibly people with a pacemaker. Even aside from direct messing with the pacemaker, losing all those bitcoin just because you wanted a cool beer could lead to medical problems.

However, there has been an advance. Wu et al. (Acta Materiala 237: 118154) have taken the Mn3SnC and coated it with a piezoelectric layer of lead zirconate titanate. Don’t ask me how they come up with these things; I have no idea, but this is certainly interesting. They probably do it by looking through the literature to find materials already known to have certain properties. Thus a piezoelectric effect is where you generate an electric voltage by applying pressure. Such effects are reversible so if you can generate a voltage by applying pressure to something, you can generate pressure by applying a potential difference. Recall that pressure also can generate a cooling effect. Accordingly, by applying an electric field to this coated material a cooling effect was obtained equivalent to that of a 3 tesla magnetic field. When the electric field is removed, the temperature returns to where it was. How useful will this be? Hard to tell right now. The temperature drop when applying a field of 0.8 kV/cm was slightly under 0.6 of a degree Centigrade, which is not a huge change while the voltage is tolerably high. Interestingly, if you apply a magnetic field you also get a temperature change, but in the opposite direction – instead of cooling, it heats. Why that is is unclear.

As you might guess, there is still a significant distance to go before we get to a refrigerator. First, you have to get the cooling into some other fluid that can transport it to where you need it. To do that you have to take the heat out of the cooling fluid, but that will heat up your unit, so you need another fluid to take the heat to where it can be dissipated. We have very roughly the same cycle as our present system except we are not compressing anything but we have two fluids. Except I rather think we will be, because pumping a fluid involves increasing its pressure so it flows. The alternative is to put the material across the rear wall of the refrigerator thus to cool the interior and have the heat dissipated out the back. The problem now is the change of temperature is rather small for the voltage. This is not so much a problem with fluids transporting it, but if the solids transport it, the solids are always heated by the environment so your temperature drop is from the room temperature. Half a degree is not very helpful, although you could increase the electric field. Unfortunately, to get a big enough temperature change you might be into the spark jumping region. Lightning in the kitchen! Finally, do you want the back of your refrigerator to be carrying even a kilovolt electric field? My guess is this effect may remain a curiosity for some length of time.

Economic Consequences of the Ukraine War

My last post mentioned the USSR collapse. One of the longer term consequences has been this Ukraine war. Currently, there have been problems of shelling of the Zaporizhzhia nuclear plant, and this appears to have happened in that our TV news has shown some of the smashed concrete, etc. The net result is the plant has shut down. Each side accuses the other of doing the shelling, but it seems to me that it had to be the Ukrainians. Russia has troops there, and no military command is going to put up with his side shelling his own troops. However, that is far from the total bad news. So far, Ukraine has been terribly lucky, but such luck cannot last indefinitely. There are consequences outside the actual war itself. The following is a summary of some of what was listed in the August edition of Chemistry World.

The Donbas area is Ukraine’s heavy industry area, and this includes the chemical industry. Recently, Russian air strikes at Sieverierodonetsk hit a nitric acid plant, and we saw images of the nitrogen dioxide gas spewing into the atmosphere.

Apparently, in 2017 Ukrainian shelling was around a chemical plant that contained 7 tonne of chlorine. Had a shell hit a critical tank, that would have been rather awkward. Right now, in the eastern Donbas there is a pipeline almost 700 km long that pipes ammonia. There are approximately 1.5 million people in danger from that pipeline should it burst; exactly how many depends on where it is broken. There are also just under  200,000 t of hazardous waste stored in various places. The question now is, with all this mess generated, in addition to demolished buildings and infrastructure, who will pay what to clean it up? It may or may not be fine for Western countries to use their taxes to produce weapons to give to Ukraine, but cleaning up the mess requires the money to go to Ukraine, not armament-making corporations at home.

The separation of the Donbas has led to many mines being closed, and these have filled with water. This has allowed mercury and sulphuric acid to be leached and then enter the water table. During 2019, a survey of industrial waste was made, and Ukraine apparently stores over 5.4 billion t of industrial waste, about half of which is in the Donbas. Ukraine has presumably inherited a certain amount, together with some of the attitudes, from the old Soviet Union. From experience, their attitude to environmental protection was not their strong point. I recall  one very warm sunny morning going for a walk around Tashkent. I turned a corner and saw rather a lot of rusty buildings, and also, unbelievably, a cloud. How could water droplets form during such a warm dry climate? The answer was fairly clear when I got closer. One slight whiff, and I knew what it was: the building was emitting hydrogen chloride into the atmosphere and the hydrochloric acid droplets were the reason for the rust.

Meanwhile, some more glum news. We all know that the sanctions in response to the Ukraine war has led to a gas shortage. What most people will not realize is what this is doing to the chemical industry. The problem for the chemical industry is that unlike most other industries, other than the very sophisticated, the chemical industry is extremely entangled and interlinked. A given company may make a very large amount of chemical A, which is then sold as a raw material to a number of other companies, who in turn may do the same thing. There are many different factories dependent on the same raw chemical and the material in a given chemical available to the public may have gone through several different steps in several different factories.

An important raw mixture is synthesis gas, which is a mix of carbon monoxide and hydrogen. The hydrogen may be separated and used in steps to make a variety of chemicals, such as ammonia, the base chemical for just about all nitrogen fertilizer, as well as a number of other uses. The synthesis gas is made by heating a mixture of methane gas and water. Further, almost all chemical processing requires heat, and by far the bulk of the heat is produced by burning gas. In Europe, the German government is asking people to cut back on gas usage. Domestic heating can survive simply by lowering the temperature, although how far down one is prepared to go during winter is another question. However, the chemical industry is not so easily handled. Many factories use multiple streams, and it is a simple matter to shut down such a stream, but you cannot easily reduce the amounts going through a stream because the reactions are highly dependent on pressure, and the plant is in a delicate balance between amount processed and heat generated.  A production unit is really only designed to operate one way, and that is continuously with a specific production rate. If you close it down, it may take a week to get it started again, to get the temperature gradients right. One possibility is the complete shutdown of the BASF plant at Ludwigshafen, the biggest chemical complex in the world. The German chemical industry uses about 135 TWhr of gas, or about 15% of the total in the country. The price of such gas has risen by up to a factor of eight since Russia was sanctioned, and more price rises are likely. That means companies have to try to pass on costs, but if they face international competition, that may not be possible. This war has consequences far beyond Ukraine.

Gorbachev: A Man for What Season?

Mikhail Sergeyevich Gorbachev is dead, and the eulogies are flowing thick and fast, but mainly from those outside Russia. He may well have the record for the most praise for someone who made the worst botch-up of the job he was appointed to do. He is praised in the West for dismantling the Soviet Union, but that was the last thing he was trying to do. He believed that liberalizing the economy would improve the lot of Russians. After he was deposed and the USSR fell, the GDP of Russia almost halved, and only too much that was left fled the country in the hands of a few oligarchs. You see comments by Bill Browder on how bad Putin is, but he made a billion dollars from the ignorance of the ordinary Russian and according to Russia, he never paid a cent in tax to Russia. Quite simply, Gorbachev gave the country that hated Russia (the US) what it wanted and completely failed Russia. He had a dream, but he never checked to see whether it was realistic, and he never had a workable plan to implement it.

Gorbachev’s early important jobs related to agriculture. The Soviet Union should have been a major food exporter, but in the 1970s, in part because of poor weather, it had to import grain. Gorbachev was supposed to do something about this, and his response was to blame central decision-making. That may well have been a factor, but it was not the required answer. I visited the USSR in the early 1980s, and in a drive through the countryside of Uzbekistan the problem was easy to see. There were huge areas of the steppe that had been ploughed, and then, nothing. Not even harrowed to at least make it look as if something was being done. But in small “oases” there was extremely intense productivity. Those in the collective were given very small areas of land for themselves to use, and basically they concentrated on that. This was where almost all the local food came from, a tiny percentage of the total land. Now, if I could see this in a short visit which was really more as a tourist (I was getting over jet lag and enjoying a weekend before heading to Moscow for what I went there for) surely Gorbachev could have found this out if he wanted to.

Part of my life has been devoted as a consultant to fixing problems, and my first rule of fixing a problem has always been, first examine the problem in intense detail and understand it. To examine it, you actually have to go and look at it yourself. Reading a report is no good unless there is a recommendation to fix it, because if whoever wrote the report does not know how to fix it, perforce (s)he does not understand it. This is probably a major failing of leaders everywhere, but it was much worse in the USSR. If the leader cannot take the time off to look at it, he should delegate to someone who can. At this time fixing agriculture was Gorbachev’s main job; he was the delegated man, and at this point he failed. The USSR kept importing food, which also was a drain on foreign currency. One could argue that the system prevented success, but Gorbachev had Yuri Andropov as a friend, and if he could persuade Andropov, almost certainly what he recommended would be done. The simple answer is the farmers had to have an incentive to increase the communal yield. That introduces the most significant problem in economics: how to properly reward people. Something needed to be tried, such as giving small groups of farmers (since they had to maintain some part of communism) the right to take shares of the yield from a block of the commune land.

When Gorbachev became effectively the leader of the USSR, he had learned nothing from his agrarian program, and while he recognized industry needed a better output and productivity, he still relied on central planning, while ignoring implementation. A plan that might work is only of use if there is a working procedure to make it work. For his plans to work, first he had to remove the many layers of bureaucrats between the major decision and implementation. His first move was to remove the “old guard”. This was a clear mistake as a first move. They knew someone younger was needed, which was why they put him there. Many should have been potential allies. His replacements included people like Yeltsin, who ended up doing everything he could to subvert Gorbachev. Gorbachev was not a good judge of character, and completely failed the next step: if you want to run a central system the top priority is to find someone who gets things done. They are seldom people who play the political game making fine speeches praising Lenin. Gorbachev tried to introduce some sort of limited private enterprise and market economics, but because of the layer of incompetents under him and his demand that central planning be retained, that did not work.

The next major blunder was “glasnost”; giving the people the right to complain. There was too much to complain about. Freedom to criticize is all very well, but if the criticisms are going to be well-grounded and nobody is fixing them, the society fragments. Gorbachev apparently thought that if the people knew about all the problems they would rally behind his efforts to fix them. That was ridiculous. The noisiest dissidents are the least constructive. He needed fixers in place before allowing people to shout out what needed fixing. After all, a lot was obvious. Again, I recall going into a building in the old USSR that was supposed to be where you bought things. The shelves were empty. Fixing food production and providing a range of consumable goods should have been the first priority. If everyone had more to purchase, and higher incomes from the increased productivity, now open criticism would be harmless.

Gorbachev made an impression on Western leaders. The nuclear disarmament treaty was an achievement, but when it came to the reunification of Germany and the USSR giving the Warsaw Pact countries their independence from Moscow control, Gorbachev badly needed to ensure that NATO did not march East. Given that he was offering a lot, he needed a signed treaty ensuring the “neutral zone”. He could have obtained that from the Eastern countries, although he probably also needed the US to agree, but for some reason he made no effort at all, which eventually brings us to the current Ukraine conflict. He was to permit some of the republics to leave the USSR, but he made no effort to settle the legal conditions of doing so, which later led to the Georgian and now Ukrainian problems. The USSR owned all the factories, etc, in the breakaway republics, but these ended up in the hands of a very few oligarchs.  Gorbachev had great ideas, but was seemingly uninterested in the details of achieving them, or of ensuring decisions were not undermined by others. The end result was the rule of Yeltsin, and the impoverishment of a very large fraction of the population, the transfer of virtually all of Russia’s industrial and resource assets into the hands of a few oligarchs, the almost halving of the nation’s GDP, and all this really followed from Gorbachev’s inept governance. Gorbachev seemed to think people would rally behind to get the best outcome. That is delusional. They follow incentives or they fly off in different directions. He failed to provide incentives or control where things went. He achieved nothing of substance for those who depended on him. He is popular with those who took advantage of him.