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NNadir

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Nobel Laureate and Nagasaki Atomic Bomb Survivor Osamu Himomura Has Died.

From Nature: Osamu Shimomura (1928–2018)

Growing up during one of the darkest times in history, Osamu Shimomura devoted his long and fruitful career to understanding how creatures emit light. He discovered green fluorescent protein (GFP), with which — decades later — biomedical researchers began to monitor the workings of proteins in living tissue, and to confirm the insertion of genes. For that discovery, he shared the Nobel Prize in Chemistry in 2008 with neurobiologist Martin Chalfie and the late Roger Tsien, a chemist.

Shimomura, who died in Nagasaki, Japan, on 19 October, was the first to show that a protein could contain the light-emitting apparatus within its own peptide chain, rather than interacting with a separate light-emitting compound. The significance of this discovery was that the gene encoding GFP could, in principle, be copied (or ‘cloned’) and used as a tool in other organisms...

...Born on 27 August 1928 in the town of Fukuchiyama, at the height of Japanese expansionism, Shimomura was the son of an army captain whose frequent postings abroad disrupted his child’s school education. Shimomura’s grandmother instilled in him the samurai principles of honour and fortitude. In 1944, with the Pacific War turning against Japan, he and his fellow school students were mobilized to work in a munitions factory in Isahaya, about 25 kilometres from Nagasaki. On 9 August 1945, he was at work when a blinding flash, followed by a huge pressure wave, signalled the dropping of the atomic bomb on the nearby city. He walked home under a shower of black rain. He later wrote that his grandmother’s quick action in putting him straight in the bath might have saved him from the effects of the radiation.

Without a high-school diploma, he despaired of finding a college place. Eventually, Nagasaki Pharmacy College admitted him in 1948. On graduation, he worked for four years as an assistant in practical classes. He devised research projects in his own time, and his professor obtained permission for him to do a year of advanced study...

...The luciferin paper brought an invitation for Shimomura to join the bioluminescence lab of biologist Frank Johnson at Princeton University in New Jersey. Three weeks after marrying Akemi Okubo in August 1960, Shimomura sailed to the United States, his travel paid for by a Fulbright scholarship...

...He discovered almost at once that it was activated by calcium (later, aequorin became an essential reagent as a glowing marker of calcium release). Shimomura, his family and his research colleagues spent 19 summers at Friday Harbor, collecting hundreds of thousands of jellyfish to obtain enough of the elusive material for a full structural analysis. Until a way of making genetically engineered aequorin became available in the 1990s, Shimomura freely shared his carefully harvested stocks with laboratories the world over...


Remarkable.

He reminds me of another Japanese scientist who labored in obscurity on a difficult project, investing heavily his own time, Shuji Nakamura (now at UC Santa Barbara).

One of my son's professors got his Ph.D. and did a post doc with Nakamura.

Nature Editorial for Scientists: Beware the rise of the radical right

The following editorial appears in the journal Nature, one of the world's premier scientific journals:

Beware the rise of the radical right

Academic freedom is on the hit list when radical politicians gain office — as they have done in Europe.

Some excerpts:

Hidden inside a 1970s office block close to London’s Waterloo station is a tiny organization that has helped tens of thousands of academics find sanctuary from conflict. Co-founded 85 years ago by the economist William Beveridge and physicist Ernest Rutherford, the organization, now called the Council for At-Risk Academics (CARA), enabled many notable twentieth-century scientists — including biochemist Hans Krebs and philosopher Karl Popper — escape the Nazis and settle at British universities. In recent years it has reached out to the Middle East and receives the largest volume of applications from Yemen and Iraq.

CARA and its counterparts in other countries exist because governments in the host nations value three of the pillars on which democracy rests: the rule of law, a free press and, as we explore in a Comment article, freedom of academic enquiry. If the British government were to decide not to support even one of these, CARA would struggle to carry on...

...Europe’s heads of government are biting their lips, and their reasons for doing so are understandable, even if European agreements or conventions are being violated. There is, of course, the principle of non-interference in the affairs of a sovereign state. But, in addition, the EU works through the collective solidarity of its member states. This is what has enabled the organization to enact progressive policies in climate change, anti-discrimination legislation and employee rights.

But collective progressivism breaks down when one-third of EU governments include political parties with scant commitment to protecting democratic institutions. Now that EU governments include parties who do not believe in the rights of people from minority groups, the consensus on climate change, or, indeed, academic freedom, it will become more difficult for the EU as a whole to either advance, advocate or protect policies in these fields...


I don't know why the editorial singles out Europe.

The United States - and now Brazil - are ruled by some of the worst examples of human beings the world has ever seen.

We will see if "the rule of law" can survive in the US. How history will regard it will depend entirely on whether the orange nightmare and his enablers see prison time or, better yet, die in prison.

The implications extend well beyond science, but at as we are realizing the climate catastrophe predicted years ago by scientists, more than science is at risk. It is the very future of humanity that is on the line.

Technetium in Use and in the Environment: Alloys, Sellafield Lobsters and Deep Eutectic Solvents.

The paper, among others, that I will discuss in this post is this one: Efficient and Selective Extraction of 99mTcO4– from Aqueous Media Using Hydrophobic Deep Eutectic Solvents (Tim E. Phelps , Nakara Bhawawet , Silvia S. Jurisson* , and Gary A. Baker,* ACS Sustainable Chem. Eng., 2018, 6 (11), pp 13656–13661)

In my late teens, I had a weekend job in a hospital pharmacy working on the distribution of IV solutions to the different hospital wings. The room in which I worked was not actually in the pharmacy, but was rather attached to the Central Supply room which was also staffed by two other teenagers, two young women - leading to all sorts of flirting but no real romance - one of whom was the niece of a prominent physician on the Hospital staff. Because of her uncle, she knew many of the doctors who worked in the hospital, including, as luck would have it, the pathologist who conducted autopsies. The pathologist, a Nisei, was an avuncular guy, and because of the connection with her uncle, that young woman was able to weasel invitations for the three of us to go to autopsies, perhaps because the pathologist was trying to stimulate interest among us kids to go into medicine or at least learn something about anatomy.

As a result, I got to watch maybe 10 or so autopsies after finishing my IV distribution work, and although I had no interest whatsoever of going into medicine, I certainly got some insight into at least one human disease, lung cancer, a disease which would later kill my father. I recall the autopsy of the lung cancer victim very well, probably much better than all the other autopsies I attended, with the possible exception of a still born baby with a three chambered heart. The pathologist was going through the lungs of the lung cancer victim and for our benefit, removed a tumor and sliced it in half to show us something very interesting, which was that at the very center of the tumor there were black particles, carbon I'd guess. Since I was worried all the time about my father - a heavy smoker who would nevertheless go on to live 20 years after these adventures of mine - I asked the pathologist if the dead man had been a smoker. "No," he replied, "smoker's lungs look much, much worse than this. This man was a teacher in New York City. This is from air pollution."

I never forgot that moment. On reflection, I think it changed my life. Thank you Dr. Araki.

Recently in this space, in an exchange with a dumb anti-nuke, if I recall correctly, I mused about the to which the idea that dangerous fossil fuels are cheap and affordable and even essential - and thus that we cannot live without them - is connected to the undeniable fact that they are routinely, without a peep, allowed to do what the nuclear industry is not allowed to do, which is to directly dump its waste products directly into the environment.

The distinction here is connected with something about which I often rail uselessly, the difference between internal and external costs. The internal cost of the dangerous fossil fuel gasoline is what you pay at the pump or at the outlet. The external cost is the cost (among others) of the people who die – often horribly, sometimes after long periods of disability - from the air pollution the combustion of your gasoline, never mind coal and gas for electricity, produces.

By contrast, the nuclear industry is held to a standard which essentially demands that no one ever be hurt or injured, much less killed by it’s by products – most commonly referred to as “nuclear waste,” although I personally don’t use that term since I insist that anything that is useful need not be “waste.”

As it happens though, the nuclear industry has deliberately released radioactive fission products in the past, most notably at the La Hague and Sellafield nuclear fuel reprocessing plants, one of which is now shut, albeit at an overall loss to humanity. The health consequences resulting from this practice would be negligible were it not for the pollution generated by people powering up their computers effectively to complain vociferously about how tragic it is that any radioactive atom exists anywhere; generally these are the same people who couldn’t care less about the 7 million people who die every year from air pollution and the fact that there are no living things on this planet that are not exposed to essentially all of the many toxic constituents of dangerous fossil fuel waste in addition to carbon dioxide.

Of course, one might argue that there are no living things on the planet which have not been exposed to fission products, for example, technetium in the form of the highly water soluble and therefore highly mobile pertechnate ion, TcO4-. This, by the way, is true. It is also true that people deliberately eat or are injected with the pertechnate ion in hopes of saving their lives, but that’s another matter on which I’ll touch below.

The processing plants at Sellafield utilize(d) the PUREX process for isolating plutonium from used nuclear fuel. This is a solvent extraction process wherein fuel rods are chopped and then largely dissolved in nitric acid. A series of solvent extractions, coupled with precise oxidation and reduction steps allow for separation of the various elements constituting fission products and actinides by selectively putting some of them in a form that makes them hydrophobic ,so that they can be extracted into the dangerous fossil fuel product kerosene containing complexing agents, the most famous of which is tributyl phosphate, although many similar complexing agents tailored for very specific target elements, for example, americium, neptunium and curium are known.

In these extractions, most of the fission products, except the precious metal fission products, ruthenium, rhodium and palladium as well as the gaseous fission products – largely krypton and xenon along with some decay generated helium-4 and sometimes small amounts of hydrogen containing three isotopes including the radioactive isotope tritium and its decay product helium-3, – remain in the acid solution. Notable constituents of this solution are the relatively long lived radioactive isotopes of cesium, iodine – chiefly iodine-129 – strontium and the aforementioned pertechnate ion.

Historically, these aqueous solutions have been problematic, and people didn’t know exactly what to do with them. At the Hanford Site in Washington State, where during the era of cold war hysteria, huge amounts of plutonium was isolated in order to manufacture nuclear weapons - these solutions were simply placed in giant tanks. The first tanks so utilized were single shell tanks from which they ultimately leaked, causing a great deal of concern and the expenditure of huge amounts of money to clean them up. The Hanford tanks are a giant bugaboo for those interesting people who freak out every time radioactivity is mentioned without even the slightest consideration of relative risk. Of course, there is no evidence that the nearby city of Richland, Washington is at risk of being depopulated by these tank leaks; there may be some elevated but as yet undiagnosed risks there; I can’t say. Perhaps the increased level risk of living in Richland is roughly comparable to the risk might approximate the risk of commuting in one’s automobile 50 miles per day instead of walking to work around the corner. Again, I can’t say, but it seems clear to me that the risks are overstated – often vastly overstated - when nuclear materials are discussed, and largely ignored when dangerous fossil fuel materials are discussed.

For a favorite example in my own discourse, one of the most stupid remarks I’ve encountered in this space came from a correspondent, now on my “ignore list,” who announced that the collapse of a tunnel containing some old chemical reaction vessels at the Hanford site “proved” that nuclear energy was “dangerous,” – even if there is zero evidence that anyone died or will die as a result of this event. Of course, the correspondent, from what I could tell, was completely disinterested in the possibility that 70 million deaths every decade, without stop, from air pollution might have some bearing on the related question of whether fossil fuels are “dangerous.” (I routinely claim that they are just that, dangerous fossil fuels, and seldom refer to fossil fuels in any other way.)

In Britain, the equivalent of the Hanford Site is the Sellafield Site on the coast of England, in Cumbria, which borders Scotland. It is the site of the world’s first commercial scale nuclear power plant,– the Russians had built a smaller plant that they connected to the grid a bit earlier – the Calder Hall reactor, which operated from 1956 to 2003, using rather (understandably) primitive technology.

Truth (an unpopular commodity) be told, though, the “primitive technology,” the carbon dioxide working fluid might prove quite interesting in the case that humanity actually got serious about climate change – there is no evidence this will actually happen – since the key to the thermochemical splitting of carbon dioxide is, as it sounds, hot (supercritical) carbon dioxide. This suggests that one could imagine a working fluid that is a continuously shifting mixture ratio of two carbon oxides, dioxide and monoxide, with periodic separations of the two, one providing carbon for use, the other turning turbines to drastically increase thermodynamic efficiency and generating some pure oxygen on the side, which also might be useful for industrial scale carbon capture from the air.

The Calder Hall Reactor was deliberately designed to be a type of reactor that made access to weapons grade plutonium possible. Obtaining weapons grade plutonium is economically wasteful, since it requires relatively short irradiation times and low burn up in order to prevent the buildup of Pu240, which greatly complicates weapons manufacture as well as reducing the yield of weapons know colloquially as “fizzle.”

“Burn up” in a nuclear reactor may be thought of as fuel efficiency, translating “miles per gallon” into “megawatt-days per ton.” The growth in US (and other countries’) nuclear power production in the 1990’s – which lead to it having the highest capacity utilization of any type of electrical generation plant - despite the disastrous US policy of abandoning nuclear plant construction infrastructure, is, along with operating experience, a function of increased burn-up, since it reduces the number of days required for refueling shut downs. The longer the burn up time utilized in a reactor at maximum power levels, the more useless the plutonium generated in them becomes for weapons manufacture. For “breed and burn” types of reactors, accumulation of Pu238 (from the buildup and decay of Cm242) makes the use of all of the plutonium completely unusable for weapons. (Cf. A new scientific solution for preventing the misuse of reactor-grade plutonium as nuclear explosive (Kessler et al, Nuclear Engineering and Design 238 (2008) 3429–3444).)

Let’s be clear as an aside: The British nuclear weapons program utilized Calder Hall weapons grade plutonium (as well as Windscale Plutonium) to make nuclear weapons. Their nuclear weapon inventory is nowhere near the scale of either the Russian or American inventory, but the recent demonstration that even in a formerly stable democracy, the control of nuclear weapons can fall into the hands of patently insane people – the existence and position of the clearly insane person Donald Trump shows that the representation of Jack T. Ripper in “Dr. Strangelove” was, and now is, not as much comedy as designed – obviates the fact that nuclear weapons must be eliminated and that no country can be trusted to possess them.

The reprocessing of used nuclear fuel for the purpose of making bomb grade plutonium with the PUREX process requires the use of far more solvents and reagents than reprocessing commercial nuclear fuel because the plutonium contained in the fuel is far more dilute. Although ultimately the British switched to the less onerous processing of commercial fuels, almost all of the initial reprocessing performed at Sellafield was for fuels being used to make weapons.

The British utilized a different approach to dealing with the aqueous raffinates containing fission products (and small residual amounts of actinides) than the American did at Hanford and the Soviets did at Mayak. After some processing, they, having a coastal plant as opposed to inland plants like Mayak and Hanford, dumped many of the fission products, along with actinide residues including plutonium, in the ocean utilizing an outfall pipe extending a few kilometers into the Irish Sea. (British Magnox fuels which were designed for simplified reprocessing, unlike American, French, and most other nations' nuclear fuel, must be reprocessed; they are not suitable for long term storage.)

For the rest of this post, I will focus on one radioactive component of this raffinate, technetium.

Technetium, which has the chemical symbol Tc, is the 43rd element in the periodic table. All of its known isotopes are radioactive. One isotope – one that is actually quite difficult to obtain – 98Tc, has a half-life of 4.2 million years, still far too short to have survived the 4.5 billion years since the accretion of the earth from the supernovae ejecta from which it formed. It is unlikely that there is even 100 grams of it on the entire planet. Any that exists has been manufactured by humanity at great expense in accelerators, or obtained in nuclear reactors at miniscule yields. The better known and more readily available isotope is 99Tc which is a major fission product when an actinide element such as uranium or plutonium, americium or curium undergoes a fission event, either spontaneously or as a result of being struck by a neutron as in a nuclear reactor. It is generally regarded as a “synthetic element,” and was, in fact, the first such element to be discovered, in 1937. That said, because uranium is a relatively common element in the earth’s crust, as common as tin, and because uranium has continuously been undergoing spontaneous fission since the formation of the earth, it is now understood that technetium does occur naturally, albeit in concentrations that are so low that it makes its detection exceedingly difficult and its isolation from natural sources nearly impossible.

The Earth’s oceans, for instance, contain – limited only by uranium’s marginal solubility in water – about 5 billion tons of uranium. The half-life of uranium’s most common isotope, 238U, is 4.468 billion years, coincidentally nearly equal to the age of the earth. The nuclear decay of uranium – which like technetium only has radioactive isotopes – usually decays by α emission, but far more rarely it also undergoes spontaneous fission. The spontaneous fission half life of Uranium-238, as opposed to its much shorter α decay half-life, is about 8 quadrillion years, meaning that the decay constant (=ln(2)/t½) for spontaneous fission is 2.8 X 10-24 sec^(-1). From this information, one can calculate that about 30 trillion atoms of uranium fission each second in Earth’s oceans. The fission yield of lighter isotopes for uranium-238’s spontaneous fission is given at the JENDL website and can be found by summing the fission yields of the predominant species with mass number 99 formed directly by fission, 99Rb, 99Sr, 99Y, 99Zr, 99Nb, and 99Mo, each one upon formation decaying by β- decay into the following member of the decay series. The sum of these yields suggests that 6.154% of the time, a nucleus with mass number 99 is formed under these circumstances. With the exception of 99Mo, which has a half-life of about 64 hours, none of these highly radioactive isotopes has a half-life exceeding 2 minutes, and all of them rapidly decay ultimately to give 99Tc which has a half-life of 211,100 years. Thus 99Tc represents a “decay bottleneck,” if you will, before itself decaying into the stable ruthenium isotope 99Ru. From the decay constant of 99Tc, which is 1.04 X 10-13 sec-1, one can calculate that the steady state quantity of 99Tc – the amount of 99Tc that can accumulate before it decays at exactly the same rate at which it is formed – in earth’s oceans arising from the natural spontaneous decay of solvated uranium is about 3.4 kilograms, distributed in all the oceans in all the world.

The amount of technetium released at Sellafield absolutely dwarfs the amount of naturally occurring technetium in the ocean. It is estimated that the total cumulative amount of technetium as of 2006 was 1700 terabequerels. (cf. An estimate of the inventory of technetium-99 in the sub-tidal sediments of the Irish Sea (Leonard et al Journal of Environmental Radioactivity 133 (2014) 40-47).) The specific activity of technetium is 0.63355 gigabequerels per gram, meaning that the total cumulative amount of technetium released into the Irish Sea was on the order of 2.7 metric tons. Although technetium PUREX raffinates all contain technetium in the +7 oxidation state, again, as the highly soluble pertechnate ion, TcO4-, it is well known from nuclear testing, nuclear accidents, and sewage treatment plants containing technetium from the urine of patients injected with the element for imaging purposes, that the pertechnate ion can be reduced by organic matter or by organisms to the insoluble oxide in the +4 state, TcO2, technetium dioxide. The paper just cited indicates that about 2% of the Sellafield releases are found in sediments in the Irish Sea, undoubtedly largely in this form.


The quantities of technetium released at Sellafield varied from year to year and exhibited large peaks and valleys. A paper on the subject of technetium releases and incorporation of the element into the edible tissues of local lobsters and crabs reports that technetium releases peaked around 1995 after a new plant, most probably using a new variant of the PUREX process, called the EARP (Enhanced Actinide Recovery Plant) went into operation in 1994. (cf. Variability in the edible fraction content of 60Co, 99Tc, 110mAg, 137Cs and 241Am between individual crabs and lobsters from Sellafield (north eastern Irish Sea) (D.J. Swift, M.D. Nicholson, Journal of Environmental Radioactivity 54 (2001) 311-326). According to this paper, the Sellafield Tc releases rose from about 5 Terabequerels on average in preceding years to 72 TBeq (114 kg), 192 TBeq (303 kg), 155 TBeq (245 kg), 84 TBeq (133 kg), and 53 TBeq (84 kg).

The authors of this paper purchased crabs and lobsters from local fishermen who were known to be obtaining their catches near the Sellafield outfall pipe on May 25, and June 5, of 1997.

The number of crabs collected was 34, with 16 females and 18 males being collected. The mean weight of the crabs was 490 grams, and the mean weight edible tissues was 148 grams.

For lobsters, 37 were collected, 20 females and 17 males. The mean weight of these animals was 654 grams - 523 grams for females, 807 grams per male, with the edible portions of each, respectively, being 160 grams and 246 grams.

In this paper, the naturally occurring radioactive isotope K-40 that is present in all of the essential element potassium on the Earth is measured as a marker for all of the other radioisotopes measured in the experiment, Ag-110m, Cs-137, Am-241, Co-60 as well as Tc-99. In crabs, the only radisotope found to be at the same order of maginitude as postassium-40 is technetium; all the others are found at an order of magnitude lower. The mean measurement for potassium-40 is 93 Beq/kg, and 126 Beq/kg for crabs, with a rather large standard deviation which is on the order of the measurement itself. The other radioisotopes are found at levels approaching their lower limit of detection, an order of magnitude smaller than potassium-40.

For lobsters, the situation is quite different.

Lobsters seem to concentrate technetium. The mean value for lobsters is 11,300 Beq/kg, reflecting 7,131 Beq/kg for male lobsters and 14,853 Beq/kg. The mean mass of edible meat of female lobsters in this sample was 160 grams, meaning that if one ate an “average” female lobster that lived its life near the Sellafield outfall pipe in the spring of 1997, one would end up eating 2,377 Beq of Technetium, without reference to the experimental error discussed at length in this paper.

I plainly confess that for about 1/3 of my adult life, I was an anti-nuke, sometimes rabid, sometimes passive, and as such, was completely divorced from critical thinking about nuclear issues and in fact I knew nothing at all, effectively, about nuclear science but nonetheless felt myself qualified occasionally to be outraged by the existence of things like the Sellafield plant. I can easily therefore imagine how a person dumb enough to say, think that the collapse of a tunnel holding old radiologically contaminated chemical vessels at Hanford suggests that nuclear power is “dangerous” on a planet where 7 million people die every year from air pollution, might view the idea of 2,377 Beq of technetium in the meat of a lobster growing up near the outfall pipe of the Sellafield nuclear reprocessing plant. One can be quite sure as well that the ship of fools belonging to that benighted organization Greenpeace, the Rainbow Warrior, cruised all around the North Sea burning diesel fuel carrying functional idiots flashing signs and banners with inane content all because of Sellafield.

The means of detection of technetium in lobster meat says nothing at all about the chemical speciation of the technetium in it, whether it is present as soluble pertechnate – which apparently behaves much like iodine biochemically – or as insoluble technetium dioxide. In the latter case, it’s not clear that any technetium ate by a lobster lover would be bioavailable and thus absorbed into the blood stream of the feasting person. But let’s consider opposite case, the pertechnate case, and assume really without any justification that all of the technetium found in a consumed female lobster is absorbed by the person eating the lobster. The biological half-life of technetium, the rate at which it is excreted, or put in cruder terms, pissed away, is well known because of its extreme technological importance in medical imagining and in cancer treatment. It is about 1 day. The reason it is so well known is that about 20 million people per year are deliberately injected with solutions containing technetium complexes. The reason this is so is not for the purpose of comparing them to Sellafield lobsters of course, but is rather intended to save their lives, or perhaps just to improve them dramatically. The technetium so injected is far more radioactive than Sellafield technetium, since it is largely a nuclear isomer of technetium-99, technetium-99m, which decays via an isomeric transition with the release of a gamma ray into the same technetium-99 at the outfall pipes of Sellafield. The radiological half-life of the decay of Tc-99m into Tc-99 is about 6 hours, and it is obtained from shipments of its parent nuclide, Mo-99, with a half life of 64 hours, prepared in research reactors.

According to the Wikipedia page for Technetium-99m, the radiological dose that is typical of at least one procedure, a bone scan, ranges from 700 million Beq to 1,110 million Beq, which the reader is invited to compare with eating a female Sellafield lobster, which would provide a dose that is 2 to 3 orders of magnitude smaller assuming complete absorption of all of the technetium the animal contains. Please note that the number of people who have eaten such lobsters is vanishingly small.

The conceit of anti-nukes who actually regard Greenpeace as an environmental organization, egged on in this belief by a credulous scientifically illiterate news media, as opposed to how I regard them, as an organization roughly comparable to an organization of anti-vaxxers, or creationists (at best), is that if one eats even one radioactive atom that has found its way into the environment as a result of the operations of nuclear energy related plants, tragedy will inevitably result.

This is a Trumpian scale misrepresentation of reality, in other words, a bald faced lie. The toxicology of any agent of environmental insult is inherently statistical. It is simply not true, for example, that everyone who is exposed to air pollution will die from it. Statistical analysis suggest that 7 million people die each year from it, but billions of people who have been exposed to it will die from something else, like say automobile accidents, gun fire, excess consumption of fried foods, malnutrition, etc, "the thousand natural shocks that flesh is heir to."

I opened this long post with a description of the dissection of lung tissue that so obviated the relationship between air pollution and fatal disease that even a teenaged kid could discern the relationship visually. No such relationship between eating lobsters captured near the outfall pipes of the Sellafield Nuclear reprocessing facility is likely to exist, and if there are any people on this planet whose cancers developed from technetium released at either Sellafield or La Hague, there is simply no way that they exceed the cancers and deaths that would have resulted if the Magnox fuel had never existed, if Britain continued to rely on coal as it did at the time that the Calder Hall reactor was built.

To wit:

One of the best evocations of critical thinking about nuclear energy was written by the late Nobel Laureate (and Stanford Professor of Physics) Burton Richter, commenting on the paper written by the anti-nuke fellow Stanford Professor Mark Z. Jacobson, who I personally regard as a useless idiot. Writing in a comment in the journal Energy and Environmental Science, Richter wrote:

What struck me first on reading the Ten Hoeve–Jacobson (T–J) paper was how small the consequences of the radiation release from the Fukushima reactor accident are projected to be compared to the devastation wrought by the giant earthquake and tsunami that struck Japan on March 11, 2011. The quake and tsunami left 20 000 people dead, over a million buildings damaged and a huge number of homeless. This paper concludes that there will eventually be a 15-130-1100 fatalities (130 is the mean value and the other numbers are upper and lower bounds) from the radiation released from reactor failures in what is regarded as the second worst nuclear accident in the history of nuclear power. It made me wonder what the consequences might have been had Japan never used any nuclear power. My rough analysis finds that health effects, including mortality, would have been much worse with fossil fuel used to generate the same amount of electricity as was nuclear generated. This conclusion will surely draw fire since it flies in the face of what many believe, and of new policy directions some propose for Japan and Germany.


For context, in December of 1952, a few years before Calder Hall went on line, about 4000 people died as a result of a serious coal pollution event, the London Smog event, resulting from cold temperatures and low wind speeds.

(cf. Richter, Opinion on “Worldwide health effects of the Fukushima Daiichi nuclear accident” by J. E. Ten Hoeve and M. Z. Jacobson, Energy Environ. Sci., 2012,, Energy Environ. Sci., 2012, 5, 8758.

The essence of the paper is that nuclear energy need not be completely free of risk in order to save lives on balance.

Balance.

From all of the above, a fair assessment of what I have written would suggest that I am perfectly OK with people dumping technetium in the ocean. This, however, is not true.

Rhenium, the cogener of technetium is a very rare, but very valuable strategic metal, the chief use of which is as an alloying agent to make “superalloys” – alloys displaying remarkable chemical resistance and structural integrity at high temperatures. Because of the lanthanide contraction, the atomic radii of technetium and rhenium are quite nearly identical, and thus the alloy properties are very similar. Rhenium is subject to depletion, and, since the world supply of uranium can be shown to be effectively infinite, it is quite possible that the world supply of technetium might well be made to outstrip the supply of rhenium, and alloy for its use in closed systems such as high temperature turbines used in combined cycle power plants, almost all of which in existence today are dangerous natural gas plants, although it is quite possible to imagine cleaner and safer nuclear plants that would utilize this same combined cycle approach to improving thermodynamic efficiency.

There are only small differences between the chemistry and metallurgy of rhenium and technetium, these differences resulting from the shielding by filled f orbitals in rhenium that are not present in technetium. The melting point of rhenium (3186 C) is higher than technetium (2157 C) and rhenium forms a volatile heptafluoride whereas technetium does not form a heptafluoride at all. Otherwise the two elements are nearly identical.

Prevented from growing as much as it would in a sane world by appeals to fear and ignorance delivered by Greenpeace types, nuclear energy has been stuck at providing consistently about 28 exajoules for more than 3 decades. While this is nearly three times as much as the combined solar, wind, geothermal and tidal so called “renewable energy” schemes have managed despite nearly half a century of mindless cheering, it is clearly not enough, since the use of dangerous fossil fuels is rising, not falling, this as the obvious dire effects of climate change are becoming more obvious, and as the accumulation of the dangerous fossil fuel waste carbon dioxide is rising at the fastest rate ever observed.

An estimate of the total accumulated technetium available in used nuclear fuels has been made and is available here:
Determination of technetium-99 in environmental samples: A review (Hou et al Analytica Chimica Acta 709 (2012) 1– 20). In this publication the authors state that up to 2006 about 140 Petabequerels of technetium had accumulated and that the growth rate of technetium is roughly 5.8 terabequerels per GWy of thermal (primary) nuclear energy production. From these figures, given the yearly average primary nuclear energy production of 28.4 exajoules, one can estimate that nuclear power plants have generated about 303 metric tons of technetium.

Of more interest to me personally than superalloys is the effect of alloying with technetium has on tungsten.

In the early 1960's, based on designs developed in the 1950's, a small test nuclear reactor having liquid plutonium fuel - actually a plutonium/iron eutectic - ran for a few years. This was the LAMPRE reactor. Since I first learned about this reactor, it's intrigued me. At the time of its development, only two metals were known that could contain liquid plutonium, since the liquid metal is quite corrosive to many metals since it dissolves them. One such metal was tantalum; the other was tungsten, both of which are high melting metals. For the actual reactor that was build and operated, tantalum was chosen because tungsten is a poorly machinable metal, particularly because it is brittle and lacks ductility, and the LAMPRE design included capsules featured the use of capsules that could only be made using a machinable metal subject to welding.

Tantalum is now understood to be a conflict metal, which means that it is mined under appalling social conditions, which sometimes include effective slavery for children. (The chief use of this rare metal is in cell phones, where it is useful to make small compact supercapacitors.) In an ethical world, its use would be constrained as much as is possible. For this reason, if one were to build reactors designed to exploit the many powerful features that liquid plutonium and/or its known binary and ternary eutectics – the ability spontaneously to separate fission products on line with in situ extractions, distillations and/or phase separations as well as the ability to instantaneously denature weapons grade plutonium to make it useless for use in weapons – one could not ethically do so using tantalum capsules.

The machinability of tungsten can be greatly improved by alloying it rhenium, but significantly more rhenium is required than is the case with commercial superalloys found in jet engines and gas turbines. Since rhenium is rare and expensive and easily subject to depletion, this does not represent a viable approach to reviving the LAMPRE concept on the industrial scale that would be required for any serious effort to both replace dangerous fossil fuels while cleansing the atmosphere of dangerous fossil fuel wastes, particularly the most dangerous of all, given the implications of climate change, carbon dioxide.

Completed in 1968, about six years after the LAMPRE project was defunded and the reactor shut down, at the Pacific Northwest National Laboratory (PNNL) where plenty of technetium was available since the laboratory is adjacent to the Hanford reservation, experiments were conducted to consider whether technetium offered the same advantages to tungsten alloys that rhenium did. The report on these experiments is here: Concluding Progress Report: A Study of Tungsten-Technetium Alloys (Nelson and O'Keefe, BNWL-865, 1968). It was found that the ductilization of tungsten by alloying with technetium had a transition temperature comparable to that of alloying with rhenium in the range of 3% to 25% technetium.

The phase diagram for the tungsten/technetium system is available on the ASTM database, and I have it in my files. The melting point of pure tungsten, 3422C, falls only to 3000C with the addition of 20% technetium.

The maximum temperature requirement for splitting carbon dioxide to get carbon monoxide and oxygen in one known system (cerium oxide catalysis) is considerably lower than this temperature, around 1400C for the oxygen generating step. The boiling point of strontium metal is 1377C, and of course, lower at reduced pressure. These facts make the properties of the tungsten-technetium alloy intriguing, and suggest that the quantities of technetium available currently – around 300 MT – are huge only if one is considering the metal as “nuclear waste” but small if one is considering the metal as a valuable alloying agent.

When I contemplate potential LAMPRE based reactor designs, I do so in imagining a “breed and burn system, reactors designed to run without refueling for significant fractions of a century. It is interesting to note, as an aside – without going into significant detail about how a tungsten technetium alloy might fit into this system – that a tungsten alloy under neutron irradiation for 7 or 8 decades would result in the transmutation of relatively inexpensive tungsten into the extremely valuable and rare metals including the aforementioned rhenium, the very valuable catalytic metal iridium, as well as osmium. Under the same circumstances, technetium would be transmuted into ruthenium and rhodium, also very valuable metals.

All of the above suggests that there are far more important things to do with technetium than to dump into the Irish Sea, thus causing some whining and crying from say, Norwegians, about detectable technetium in the coastal seas where they drill for oil and gas, the waste products of which end up in the flesh of every living thing on this planet while completely destabilizing the planetary climate.

(Norwegian caterwauling about Sellafield technetium, funded by the Norwegian ministry of fisheries, can be found here: Technetium-99 Contamination in the North Sea and in Norwegian Coastal Areas 1996 and 1997 (Brown et al StrålevernRapport 1998:3))

It is difficult to say what the energy demand of a world that was both sustainable and ethical might be. Current world energy demand, as of 2017, according to the most recent World Energy Outlook published by the International Energy Agency a few weeks ago was 584 exajoules. For a wild guess, let’s say that a world in which the dual goals of eliminating world poverty, eliminating the use of dangerous fossil fuels, and cleaning up the planetary atmosphere by removing much of the dangerous fossil fuel waste carbon dioxide from it – all these goals are synergistic – world energy demand might be on the order of 750 exajoules/year. To achieve these goals, in my view, all of the world’s energy would need to be obtained from nuclear energy, not necessarily via an electricity intermediate, but rather in a very highly thermodynamic efficient manner, wherein electricity might only be a side product from the use of primary nuclear energy to drive chemical reactions and separations.

It is certainly possible to estimate where the secular equilibrium between the formation of technetium and its rate of decay and/or transmutation as a reactor material might lie. (The secular equilibrium point is the point at which technetium would be decaying and/or transmuting at exactly the same rate it is being formed; all radioactive nuclei undergoing formation have such a point, representing the maximal amount that can accumulate.) I have neither the time nor the resources accurately and conveniently to do this estimation, but no matter. This said, using the calculations of the type above, and the Beq/GWy conversion factor, we can estimate that at 750 exajoules/year produced by nuclear fission using U-238 as a fuel in “breed and burn” reactors, roughly 220 tons could accumulate in a single year, and be available for use. The long half-life of Tc-99 suggests that it would be possible to obtain considerable quantities of this valuable metal, surely enough to displace rhenium demand for almost all closed systems demanding its alloys.

To achieve this goal, it is important that as little technetium as is possible be lost to waste, either in seawater or in waste dumps of any kind.

This brings me finally to the paper cited at the beginning of this post, the paper on the extraction of technetium from aqueous solutions using deep eutectic solvents, a capability that, along with separations of other radionuclides, might have well eliminated the need for the wasteful and unpopular Sellafield outfall pipe. (Tim E. Phelps , Nakara Bhawawet , Silvia S. Jurisson* , and Gary A. Baker,* ACS Sustainable Chem. Eng., 2018, 6 (11), pp 13656–13661, cited at the outset.)

For the uninitiated, the authors describe, in their opening paragraph, what a deep eutectic solvent is:

Deep eutectic solvents (DESs) represent an intriguing, potentially sustainable, and unexplored opportunity… …DESs are fluids comprised of components self-associating via complex, dynamical, and correlated hydrogen-bonding networks to produce a eutectic mixture with a melting point below that of its individual components.16−19 Although a typical DES consists of a 1:2 molar ratio mixture of hydrogen-bonding acceptor (HBA) and hydrogen-bonding donor (HBD) species (e.g., choline chloride coupled with urea: a standard DES referred to as reline), unconventional DESs including halide-free examples20 and hydrophobic (water-immiscible) versions have recently emerged as well.


They continue:


In the present communication, we demonstrate for the first time the efficient and selective extraction of trace 99mTcO4 − from aqueous solutions using hydrophobic DESs. The component structures of the three hydrophobic DESs were varied by the choice of HBA cation (trihexyltetradecylphosphonium, [P14,666 +], or tetraoctylammonium, [N8888 +]) and fatty acid as HBD species (hexanoic or decanoic acid), combined in a 1:2 (HBA/HBD) molar ratio (Figure 1). We note that the DES comprising 1:2 [N8888][Br-]/[DecA] (denoted DES B in this communication) has already been reported and characterized previously.21


A picture from the paper showing the structures of these deep eutectic solvents might clarify any difficulty associated with the chemical names:



The caption:

Figure 1. DESs examined for 99mTcO4 − extraction capability. DES A consists of a 1:2 molar ratio of trihexyltetradecylphosphonium chloride ([P14,666][Cl]) and decanoic acid (also known as capric acid); DES B consists of a 1:2 molar ratio of tetraoctylammonium bromide ([N8888][Br]) and decanoic acid; DES C comprises a 1:2 molar ratio of [N8888][Br] and hexanoic acid (caproic acid).


The use of these solvents is investigated for two purposes: One is to recover technetium from aqueous processing solutions and the other is to remove it from contaminated environmental matrices, for example groundwater. For this reason, the authors investigate its use in the presence of many common anions, chloride, phosphate, nitrate, carbonate, etc. They also add perrhenate to the equation to examine their utility in separating these two closely related species.

The measure the extraction efficiency and distribution coefficients (measures of the selectivity of the extractions) they use very dilute solutions, and utilize Tc-99m, not Tc-99, because of its higher activity, and thus ease of detection, in very dilute solutions.





The caption:

Figure 2. Percentage of 99mTcO4 − extracted by hydrophobic DESs A−C after 60 min of extraction at 25 °C for a 1:1 (v/v) ratio of DES to aqueous phase while stirring at 2000 rpm. The aqueous phase contained 0.15 M of the following competing anions; left to right: HCO3 − (brick red), Cl− (orange), NO3 − (blue), H2PO4 − (pink), SO4 2− (purple), I− (yellow), or ReO4 − (green). Five μL aliquots from each sample were counted for quantification (n = 3).


The distribution ratios are also very high:



The caption:

Figure 2. Percentage of 99mTcO4 − extracted by hydrophobic DESs A−C after 60 min of extraction at 25 °C for a 1:1 (v/v) ratio of DES to aqueous phase while stirring at 2000 rpm. The aqueous phase contained 0.15 M of the following competing anions; left to right: HCO3 − (brick red), Cl− (orange), NO3 − (blue), H2PO4 − (pink), SO4 2− (purple), I− (yellow), or ReO4 − (green). Five μL aliquots from each sample were counted for quantification (n = 3).


The effect of volume ratios and time of extraction is examined.

Volume:



The caption:

Figure 4. Distribution ratios of 99mTcO4 − after a 60 min extraction at 25 °C (2000 rpm) using (A) 1:10, 1:20, and 1:50 (v/v) ratios of DES to aqueous phase containing 0.15 M I− or using (B) 1:5 and 1:10 (v/ v) ratios of DES to aqueous phase containing 0.15 M ReO4 −. Entire samples were counted for quantification (n = 3).


Time:



The caption:

Figure 5. Distribution ratios of 99mTcO4 − after 0, 5, 10, and 60 min extractions at 25 °C for a 1:50 (v/v) ratio of DES A to aqueous phase containing either 0.15 M HCO3 − (brick red) or 0.15 M Cl− (orange). Also shown are results for a 1:5 (v/v) ratio of DES A to aqueous solution containing 0.15 M ReO4 − (green). Entire samples were counted for quantification (n = 3).


However back extraction, recovery of the technetium from the deep eutectic solvent using another solvent solution is somewhat problematic, at least for the few solvents explored:



The caption:

Figure 6. Percentage of 99mTc back extracted from hydrophobic DESs A−C after 3 h at 25 °C using 0.500 mL solutions containing 0.15 M citrate, 0.1 M HCl, and 5 mg/mL Sn(II) reducing agent (pH 5). DESs used in these experiments were previously used to extract 99mTcO4 − from 0.15 M Cl− (1:50, v/v) or 0.15 M I− (1:10, v/v) aqueous solutions. Entire samples were counted for quantification (n = 3).


In their conclusion the authors refer to this problem and propose, but do not claim to have explored alternative solutions to this problem:

In summary, hydrophobic DESs comprising a 1:2 molar ratio of a tetraalkylammonium (or tetraalkylphosphonium) halide and a monocarboxylic acid are demonstrated to be excellent media for the extraction and separation of trace 99mTcO4 − in the presence of a variety of competing anions within 5−60 min at 25 °C. The partitioning efficiency of 99mTcO4 − was competitive with, or more efficient than, many previously known extraction methods and is dependent upon factors such as the nature of the competing anion(s), choice of HBD constituent, and solution pH. Importantly, anions commonly found in the environment (i.e., HCO3 −, Cl−, NO3−, H2PO4 −, and SO4 2− do not impede 99mTcO4 − extraction. Unsurprisingly, the ReO4 − anion suppresses 99mTcO4 − extraction when present in stoichiometric amounts relative to the DES. Attempts at back extraction showed limited success, although a number of avenues (e.g., Zn reduction, electrodeposition) can be considered for sequestering 99Tc from the spent DES in the future.

Given their favorable properties and low extraction volumes required, the current results have important ramifications for emerging applications using hydrophobic DESs for the extraction and separation of important tetra-oxo anions and radionuclides listed as priority pollutants by the U.S. Environmental Protection Agency, particularly for removing low levels of TcO4 − from contaminated groundwater and potentially for remediating other metalate pollutants such as perchlorate as well...


In their conclusion they also discuss certain modified PUREX like solvent extraction procedures, and the potential utility of their system for cleaning up solvents utilized in it.

I should say that personally, I'm not a solvent extraction (PUREX, UREX, TRUEX…) kind of guy in general, and prefer the development pyroprocessing electrochemical approaches given recent improvements in the electrochemical reduction of metal cations to the metals. My ideas about these processes, involving esoteric molten salts of various types, however may include liquid membranes as separation tools, and thus the existence of ionic liquids, which these deep eutectic solvents are a subset, demonstrating immiscibility with aqueous solutions are always of interest to my ruminations on this topic.

I realize that this post is fairly technical and long, and that few people will read it, and fewer will derive any value from it. My real purpose in writing it was not to convince anyone of anything - where nuclear issues are concerned, most people regrettably have closed minds, much to the detriment of humanity, and, or course, the environment - but rather to clarify and expand on some old ideas in my own mind.

A few paragraphs in this post have come from the saved text of another post I posted elsewhere on the internet, but which has disappeared, probably because the website on which I posted it (Energy Collective) has been acquired and archives have been deleted. That post focused primarily on the use of technetium in superalloys, since I was not even aware of issues in the LAMPRE reactor at that time, and had given no thought at all to the machinability of tungsten.

I personally had a wonderful weekend. Both of my sons came home to visit us and I got to spend lots of time with them and with my wife and extended family.

I trust and hope yours was as wonderful as mine.







A Return to Extraordinary Weekly Year to Year Increased CO2 Readings at Mauna Loa: 11/11/18

I keep a spreadsheet of weekly readings at Mauna Loa which calculates the difference (almost always positive) between a particular reading and the same reading of the same week the year before.

There are 2,233 such readings as of this writing, stretching back to May 25, 1975.

The top 50 readings range from a 5.04 ppm increase in a single year, recorded on July 31, 2016, to a 3.60 ppm increase recorded on May 26, 2013.

Twenty-eight of the top 50 occurred in 2016, which was an El Nino year.

This makes up the bulk of the 30 out of top 50 recorded in the last 5 years. There were two readings in this class in 2017, a post El Nino year. Thirty-six of the top 50 occurred in the last 10 years. Thirty-nine of the top 50 occurred in the 21st century.

Eight of the top 50 occurred in 1998, also a El Nino year, during which huge swathes of the South East Asian Rain Forest burned when fires set to clear forest to create palm oil plantations for "renewable" biodiesel fuel went out of control.

Two readings in 1988 were in the top 50.

One was in 1980.

2018 has been a post El Nino year; typically these are milder in terms of carbon dioxide increases to the El Nino years themselves. There were actually three readings in 2018 that recorded rises as compared to the same week of the year before that were less than 1.00 ppm, something not observed since 2015, when one such rise was recorded.

Well, finally, in 2018 we've got a figure breaking into the top 50. The week ending 11/11/2018 recorded a value of 3.63 ppm over the same week last year. It is the 28th highest increase out of 2,233 readings.

Some people think that solar and wind energy will save the day. They have not saved the day; they aren't saving the day; and they won't save the day. The reason is physics.

I recently referred to the most recent 2018 World Energy Outlook, published a week ago by International Energy Agency (IEA).

That post, which was largely, as I expected, ignored because um, truth is unpopular - especially when couched in a sarcastic title - is here: 2018 World Energy Outlook: Solar and Wind Grew by 11.24% in 2017; Gas by "Only" 3.32%!!!!

It reported that world energy consumption rose from 2016 to 2017 by 8.88 exajoules. Of that 8.88 exajoules, the bulk of it came from increases in the use of dangerous natural gas, which grew by 4.19 exajoules. (Coal based energy production, which some people report as "dead" - even though it remains the fastest growing source of energy in the 21st century - fell by a paltry 0.21 exajoules. It's not "dead." It's not even ill. It still produces 157.01 exajoules out of the 582.84 exajoules reported by the IEA, and is exceeded only by oil, which provided 185.68 exajoules in 2017, an increase of 1.97 exajoules.)

The combined solar, wind, geothermal, and tidal energy on which humanity has foolishly chosen to bet the planetary atmosphere, grew by 1.21 exajoules, and thus grew less than dangerous petroleum did, less than dangerous natural gas did. It did record an insignificant milestone however. For the first time, these four forms of so called "renewable energy" - even if the material requirements make anything other than "renewable" exceeded 10 exajoules: 10.63 exajoules to be exact.

The reading at Mauna Loa for the week ending 11/11/18 was 408.72 ppm.

No one now living will ever see a reading there of under 400 ppm again.

I'd like to congratulate all those people who carried on using gas and coal powered computers in this century about how "dangerous" nuclear energy is. I'd like to ask some of them, "Compared to what?" but there's no point in it. Experience teaches that their definition of "danger" does not include the 7 million people who died from air pollution in 2017. Because of their confused and selective attention, nuclear remains pretty static, having been producing around 28 exajoules of primary energy consistently throughout the 21st century, all the while accompanied by cacophony by scientific illiterates about how it "has to go." Were it not for fear and ignorance, it might have done more to save lives and fight climate change, but that was not to be.

The die is cast.

Have a wonderful Thanksgiving.



An interesting discourse on the biological marine sulfur cycle.

The paper I'll discuss in this post is this one: The metabolite dimethylsulfoxonium propionate extends the marine organosulfur cycle (Kathleen Thume, Björn Gebser, Liang Chen, Nils Meyer, David J. Kieber & Georg Pohnert, (Nature Volume 563, pages 412–415 (2018))

When I was a kid, one of my first professional successes in the lab involved the hydrophobic amino acid methionine, which is one of two of the 20 proteogenic amino acids (21 if one counts bacteria) for which genetic codons exist. Methionine is one of two members of this class which contains sulfur, the other being cysteine.

The role of cysteine, a thiol, in proteomics is spectacular, since its oxidative interaction with other cysteines in proteins is responsible for disulfide bridges without which many proteins would be useless, lacking the requisite geometry, and almost equally important, its role in metal co-ordination at catalytic centers of very important proteins. Methionine, a thioether rather than a thiol is far more rare in proteins, although it is important in the transfer of methyl groups in biological interactions and it has recently been discovered that interactions with the π systems in phenylalanine, tyrosine and - who knows - histidine also serve to stabilize protein geometry. Bacterial methionine biosynthesis (Ferla and Patrick, Microbiology (2014), 160, 1571–1584).

I am also interested in the chemistry of sulfur, because my generation failed all future generations by turning out planetary atmosphere into a vast waste dump for the dangerous fossil fuel waste carbon dioxide, and I am always thinking about ways that future generations can clean up our mess, and do so with a functionally destroyed resource base consisting almost entirely of our solid phase garbage dumps. One path to removing carbon dioxide from the atmosphere is to essentially reverse combustion by making the source of carbon materials - now made from dangerous fossil fuels - carbon oxides obtained by the thermal reformation (gasification) of waste (or problematic) biomass, using nuclear energy as the primary energy source. These technologies are being widely explored but a consistent factor that engineers must address is the fate of heteroatoms in biomass like potassium, sodium and, relevant to this discussion, sulfur.

Finally the paper cited at the outset of this post caught my eye because I always wonder about the environmental fate of common laboratory chemicals - one of which is dimethylsulfoxide - a wonderful solvent with wide use - and also because of my interest in stable charged organic species that play a role in a rapidly developing area of chemistry, ionic liquids.

So the paper itself:

From the abstract:

Algae produce massive amounts of dimethylsulfoniopropionate (DMSP), which fuel the organosulfur cycle1,2. On a global scale, several petagrams of this sulfur species are produced annually, thereby driving fundamental processes and the marine food web1. An important DMSP transformation product is dimethylsulfide, which can be either emitted to the atmosphere3,4 or oxidized to dimethylsulfoxide (DMSO) and other products5...


So it turns out that DMSO, which is used in some products for joint pain, is a normal biological species, present in the oceans on what may be a million ton scale. (I had a neighbor - to whom I stopped speaking years ago - who called me up to ask me if he could sue his employer because they asked him to work with this chemical, but that's another story.) That makes me feel better about all the DMSO I've used - or asked scientists working for or with me to use - in my career, for solvation, Swern oxidations, blah, blah, blah...

From the introduction to the paper:

The marine organosulfur cycle is fuelled by small sulfur-containing zwitterionic osmolytes that are primarily produced by planktonic algae. The main metabolite of this class, DMSP, is produced in the impressive amounts of 2 petagrams (2 × 109 tons) sulfur annually1. Cellular DMSP serves important physiological functions in marine algae that include, but are not limited to, acting as an osmolyte, a cryoprotectant and an antioxidant6,7. Enzymatic lysis of DMSP by DMSP lyases in bacteria and algae yields acrylate and dimethylsulfide (DMS)8. Volatile DMS is the main source of organosulfur in the atmosphere; and with an annual flux of approximately 30 teragrams of sulfur3, DMS has been proposed to affect cloud formation and regulate climate4. Dissolved DMSP arising from exudation, grazing, viral lysis and cell mortality serves as substrate for marine microorganisms7,9,10. In surface waters, substantial quantities of dissolved DMSP and DMS can be detected, but often the concentration of dissolved DMSO exceeds the concentration of each of these two species5,11. DMSO is mainly produced from bacterial and photochemical DMS oxidation12, but algal sources of DMSO may also be important13 The marine organosulfur cycle is fuelled by small sulfur-containing zwitterionic osmolytes that are primarily produced by planktonic algae. The main metabolite of this class, DMSP, is produced in the impressive amounts of 2 petagrams (2 × 109 tons) sulfur annually1. Cellular DMSP serves important physiological functions in marine algae that include, but are not limited to, acting as an osmolyte, a cryoprotectant and an antioxidant6,7. Enzymatic lysis of DMSP by DMSP lyases in bacteria and algae yields acrylate and dimethylsulfide (DMS)8. Volatile DMS is the main source of organosulfur in the atmosphere; and with an annual flux of approximately 30 teragrams of sulfur3, DMS has been proposed to affect cloud formation and regulate climate4. Dissolved DMSP arising from exudation, grazing, viral lysis and cell mortality serves as substrate for marine microorganisms7,9,10. In surface waters, substantial quantities of dissolved DMSP and DMS can be detected, but often the concentration of dissolved DMSO exceeds the concentration of each of these two species5,11. DMSO is mainly produced from bacterial and photochemical DMS oxidation12, but algal sources of DMSO may also be important13. Common pelagic bacteria use monooxygenases to oxidize DMS to DMSO14, a process that may serve as an energy source15. Here we report on the identification of the zwitterionic metabolite DMSOP, which is widely distributed in phytoplankton and also produced by marine bacteria. This metabolite is the substrate of a previously undescribed marine pathway for DMSO production (Fig. 1) .


It's probably now time to just look at the pictures the authors use to describe their "zwitterionic" species. (A zwitterion is a molecule that possesses, in the same molecule, both a positively and a negatively charged ion. The important physiological molecule carnitine is an example of a zwitterion.)

A picture:



The caption:

DMSOP and the transformations labelled with red arrows extend the established marine sulfur cycle. DMSOP is produced in eukaryotic microalgae (green) as well as in bacteria (purple). Bacteria metabolize DMSOP and therefore contribute to the marine DMSO pool. The established DMSP-based part of the sulfur cycle is indicated with grey arrows. DMSP is formed by marine algae and bacteria. It is then cleaved by algal and bacterial DMSP lyases to DMS and acrylate (not shown). The subsequent biological and photochemical oxidation of DMS to DMSO, sulfate and other products can occur within algae, bacteria, in the seawater and the atmosphere.


A picture describing some of the techniques they used to find out about DMSOP:



The caption:

a, Chromatographic profile of zwitterionic metabolites from a P. minimum culture, separated using ultra-high-pressure liquid chromatography (UHPLC) with detection by electrospray ionization mass spectrometry (ESI-MS). The total ion current is shown in grey. The metabolites glycine betaine (GBT, cyan), dimethylsulfonioacetate (DMSA, orange), DMSP (black) and gonyol (blue) were assigned according to a previous study16. The ion trace of DMSOP, red, is shown at a tenfold magnification. b, Synthesis of authentic (labelled) DMSOP. c, Mass spectrum and tandem mass spectrum (inset) of DMSOP with characteristic fragments. d, UHPLC profile monitoring m/z = 151 of an extract of P. parvum (solid line) and the same extract treated with synthetic DMSOP in roughly equal amounts (dashed line), the experiment was repeated three times with varying concentrations of synthetic DMSOP to confirm co-elution.


Biosynthetic pathways:



The caption:

a, High-resolution mass spectrum of DMSOP obtained from P. bermudensis incubated for 24 h with 13C2-labelled DMSP (Fig. 2). The peak labelled in red represents 13C2-labelled DMSOP, the natural DMSOP isotopes are shown in black (see also Extended Data Table 3). b, c, DMSO release (concentration (c) given as mean ± s.d.) of the bacteria Sulfitobacter sp. and R. pomeroyi incubated with 1 µM DMSOP. P values directly over bars indicate significant difference from t = 10 min of the same treatment, P values over brackets indicate significant difference between treatment and the control without DMSOP addition. n = 4 independent biological replicates for 24 h, n = 3 for 10 min and 5 h, for statistical details see Methods.


From the conclusion:

Our results demonstrate that the ubiquitous zwitterionic metabolite, DMSOP, contributes to the marine DMSO pool and may partly account for DMSO in marine algae13. In light of our findings, a functional role of DMSP as an oxygen acceptor is probable and could explain numerous observations of DMSP regulation under oxidative stress. Algal and bacterial DMSOP biosynthesis and its bacterial degradation to DMSO represent a previously undescribed pathway for DMSO production, extending our current paradigm of the marine sulfur cycle beyond the established biotic and photochemical pathways through DMS oxidation



Esoteric things like this are actually very important, particularly in light of the disturbance to the sulfur cycle represented by the rapidly increasing use of dangerous fossil fuels as we all wait, like Godot, for the grand "renewable energy" "revolution" that never comes.

I wish you a very pleasant weekend, and hope your Thanksgivings plans are proceeding nicely.

Science candidates prevail in US midterm elections.

I had the privilege of having a Congressperson who was a scientist - Rush Holt - until he retired. Before being elected to Congress, Dr. Holt was the Assistant Director of the Princeton Plasma Physics labs.

While I didn't always agree with everything he said or did, overall he was a magnificent congressperson, the best Congressperson I ever experienced by orders of magnitude, which is not to say that his replacement, Bonnie Watson Coleman is a bad Congressperson, only that Rush Holt was the best, by far.

He should have been our Senator, but didn't come close in the only race he entered; won by Corey Booker; Rush wasn't flashy, just solid, decent, extremely intelligent, thoughtful, concerned with justice, open, helpful and responsive.

(For the record, the worst Congressperson I ever had was Randy "Duke" Cunningham, who happily went to prison directly from Congress.)

My tempered joy aside, it appears that our new congress will include several scientist/legislators. From Nature:

Science candidates prevail in US midterm elections (Jane J. Lee,
Amy Maxmen, Jeremy Rehm & Jeff Tollefson Nature 563, 302-303 (2018))

The results of the political experiment are in. At least 11 candidates with backgrounds in science, technology, engineering or medicine won election to the US House of Representatives on 6 November — including several who had never before run for political office.

They include Elaine Luria, a US Navy veteran and nuclear engineer in Virginia, and Chrissy Houlahan, a former business executive with a degree in engineering, in Pennsylvania. Illinois saw wins by registered nurse Lauren Underwood, a former senior adviser to the Department of Health and Human Services, and clean-energy entrepreneur Sean Casten, who has degrees in engineering and biochemistry.

The four — all Democrats — are among roughly 50 candidates with science backgrounds who ran for the House in 2018, sparked in part by opposition to President Donald Trump. Fewer than half of these novice politicians made it past the primaries to the general election, but many science advocates are already looking to the next campaign cycle.

“I’m feeling good,” says Representative Bill Foster (Democrat, Illinois), a physicist who has pushed to increase the number of scientists in elected office. Foster, the only current member of Congress with a science PhD, is excited about wins at the state and local levels by candidates with backgrounds in science, technology, engineering or medicine (STEM).


I am personally pleased to see a Democratic nuclear engineer elected, which is why I bolded her discipline in the excerpt above. If I have any difficulty with my fellow Democrats, it is with those who promote what I regard as our creationism, anti-nukism, which marks us a climate change hypocrites, too prevalent in the party to which Nobel Laureate Glenn Seaborg proudly belonged - he headed the AEC when most of our life saving nuclear infrastructure was built - is finally going the way of other anti-science stuff one hears, anti-vax, anti-GMO, etc., etc, that have also represented poisoned wings of our party.

We have no hope, absolutely no hope, of addressing the most severe environmental crisis experienced by human civilization without nuclear energy. I'm glad someone's there who can understand this.

If there's any civil lining on the reign of the orange naked emperor, it is that his attacks on science have raised awareness among scientists of what the stakes are, a new dark and poisoned age, or an age in which knowledge and intellect triumph.

Congrats to our new STEM scientist/congresspeople.

2018 World Energy Outlook: Solar and Wind Grew by 11.24% in 2017; Gas by "Only" 3.32%!!!!

We're Saved!!!!

Right? Right?

I have before me a PDF of the World Energy Outlook for 2018, which was released by the International Energy Agency yesterday.

I also have opened a PDF of the World Energy Outlook for 2017, which I have discussed in many threads in this space.

The data I will discuss here is collected from World Energy Outook 2018, Table 1.1 Page 38 and, for World Energy Outook 2017, Table 2.2 Page 79.

In each case, the data refers to the year before the title year, that is WEO 2018 refers to 2017's data; WEO 2017 refers to 2016. (In earlier editions of the WEO, the lag was 2 years and not 1 year, but reporting has apparently grown quicker.)

These tables give values in "MTOE," or "Million Tons Oil Equivalent." In my discussion, as my habit, all data will be converted to the SI unit the Exajoule, except of course, that wonderful "percent talk" used here by people who still believe that it was a good idea to bet the future of every generation to come, the climate, the planetary atmosphere on so called "renewable energy."

The tables break so called "renewable energy" into three categories, hydro, bioenergy, and "other," "other" referring to solar and wind primarily, with a little tidal and geothermal presumably thrown in. In the title of this post I have ignored tidal and geothermal - which I know to be trivial with respect to solar and wind.

In 2016, "other" renewables, again chiefly solar and wind, produced 9.42 exajoules of energy. In 2017, they produced 10.63 exajoules. In "percent talk" this represents the growth of 11.42% as described in the title. In terms of energy, the growth, which can be found by using an operator called "subtraction" was 1.21 exajoules. In 2016 dangerous natural gas produced 125.90 exajoules of energy; in 2017 it produced 130.08 exajoules. In "percent talk" this represents a growth of 3.32% as described in the title here. Of course, in absolute terms, dangerous natural gas grew by 4.19 exajoules.

In "percent talk," gas thus grew 100 * 4.19/1.21 = 345% faster than wind and solar combined.

Overall, world energy consumption grew from 576.10 exajoules in 2016 to 584.98 exajoules in 2018, or 8.88 exajoules.

World energy consumption thus grew 8.88/1.21 * 100 = 731% faster than solar and wind.

What I personally regard as the only sustainable form of energy on the planet, albeit an unpopular form of energy, nuclear energy, grew by 0.29 exajoules, or only 0.29/1.21 * 100 = 24% as fast as solar and wind.

The mistake of confusing what is popular with what is right is known as the logical fallacy of appeal to popularity or at other times the "Bandwagon Fallacy."

The example in the link just presented of the "Appeal to Popularity" fallacy is this:

A 2005 Gallup Poll found that an estimated 25% of Americans over the age of 18 believe in astrology—or that the position of the stars and planets can affect people's lives. That is roughly 75,000,000 people. Therefore, there must be some truth to astrology!


In the last ten years, 2.3 trillion dollars has been "invested" in solar and wind energy:

Frankfurt School/UNEP Global Renewable Energy Investment, 2018, Figure 3, page 14

This is more than the gross national product of India, a nation with 1.3 billion people in in it.

On the planet as a whole, 2.3 billion people lack access to any kind of improved sanitary facilities; but no one is going to spend 2.3 trillion dollars to change that, not while we can all dream of solar and wind powered Tesla electric cars.

For the Week Ending November 4, 2018 (Accessed 11/14/18) the concentration of the dangerous fossil fuel waste carbon dioxide in the planetary atmosphere as measured at the Mauna Loa observatory was 406.99 ppm. In the same week 10 years ago, the concentration was 383.80 ppm.

No one now living will ever see a measurement at this site of below 400 ppm again, no matter how many miles Bill McKibben drives in his Prius with a "350.org" bumper sticker on it.

We have not been saved by the 11.24% growth in solar and wind in 2017, and are not being saved by it, and no such "percent talk" announcements in the future will represent us being saved.

We are clueless.

Facts matter.

Have a nice day tomorrow.

A Device For Air Capture of Carbon Dioxide Which Regenerates at Waste Heat Temperatures.

Events in the United States and Brazil - and in fact, practically everywhere else on Earth - in the last few years assure that every living being on Earth is going to face increasing catastrophe from climate change.

Coupled deliberate indifference by politicians, again notable in the US and Brazil, is the idiotic and unworkable misplaced but popular faith in so called "renewable energy" - which is neither "renewable" nor sustainable - that is often incorrectly described as "doing something" about climate change.

We are doing nothing about climate change.

Future generations will need therefore to find a way to clean up our mess, and do so with far reduced resources, because in our contempt for all future generations, we have been consuming vast amounts of resources for quixotic things like wind turbines and electric cars, as well as a lot of other consumer junk.

To clean up our mess, the only option for these future generations from whom we've stolen, well, everything will be - and it is an incredibly difficult engineering challenge - air capture of carbon dioxide.

About 7 years ago, a controversial but much discussed paper on the energetics and thermodynamics of air capture was published, which at least put the challenge in perspective. It is here: Economic and energetic analysis of capturing CO2 from ambient air, (House et al PNAS, 108, 51 20428–20433, 2011). It drew a negative conclusion about the possibility of doing this, by exploring an estimations the costs of various technologies for doing this:

CO2 cost per ton (House PNAS 108 51 20428–20433 2011):

Advanced nuclear: $286/ton

IGCC CSS: $666/ton

Gas CC CCS: $388/ton

Wind (land): $369/ton

Wind Offshore: $598/ton

Solar PV: $1,030/ton

Solar Thermal: $686/ton

Biomass: $580/ton

Hydroelectricity: $299/ton.


It is possible to hydrogenate carbon dioxide to make gasoline. I covered this topic elsewhere (in a place where I was banned for telling the truth): How Much Gasoline Could Hydrogenation of ONE Coal Plant's Waste Produce?

Using a similar calculation of cost, I have calculated - using 2,4 dimethylpentane as the model gasoline compound - what the cost of the carbon atoms in gasoline might translate in familiar terms in the US, dollars per gallon. (Note this does not include the internal and external costs of producing hydrogen and thus is only a fraction of the real cost of gasoline would be in this case. These costs would be, respectively, using the figures above:

$2.32/gallon, $5.40/gallon $3.15/gallon $2.99/gallon $4.85/gallon $8.36/gallon $5.57/gallon $4.71/gallon $2.43/gallon.

The House paper has been criticized in the same journal on the grounds that the analysis relied on a narrow focus on technology.

Another paper in the same journal argued that air capture is essential; it MUST BE DONE.

I personally agree with the last paper's claim, if the future generations from whom we've stolen everything are to save anything left to be saved.

Thus I was entranced by a recent publication in one of my favorite scientific journals, this one: The Development and Validation of a Closed-Loop Experimental Setup for Investigating CO2 and H2O Coadsorption Kinetics under Conditions Relevant to Direct Air Capture (Jovanovic, Ng, and Yang, Ind. Eng. Chem. Res., 2018, 57 (42), pp 13987–13998.

I have convinced myself that the only sustainable option for providing the energy for this extremely challenging engineering task is nuclear energy, although I'm not convinced that the "advanced nuclear" House describes is really suitable for the task. Few details are provided directly in the paper about the kind of nuclear energy that constitutes "advanced nuclear" in House's paper, but I suspect it involves an electricity intermediate energy form, which, in my view, is unnecessary and wasteful. Carbon dioxide and water splitting by thermochemical means involves high temperatures, and high temperatures, although increasing thermodynamic efficiency, imply the rejection of heat to the environment. To the extent that this waste heat can be partially captured to do useful things, like say, capture carbon dioxide and release it in a concentrated form available for use, it can be environmentally attractive. Hence my interest in the Jovanovic paper where the regeneration of the absorbent occurs at a relatively low temperature, 95C, temperatures which would be relatively accessible for very high temperature nuclear reactors being utilized to either split carbon dioxide or water or both.

From the introduction to the Jovanovic paper:

Over the past decades, the emission of CO2 to the atmosphere has been increasing at an alarming rate. To mitigate the resulting adverse greenhouse-effect, significant effort has been dedicated to the sequestration of CO2 from large anthropogenic point-sources such as fossil fuel-based power plants.1 However, in order to reduce the CO2 concentration in the atmosphere to the target of 350 ppm,2 it appears necessary to also capture a part of the CO2 already dispersed in the atmosphere as a product of fossil fuel combustion in the transportation sector.3 Compared to the atmospheric CO2 removal methods such as afforestation, increase of cloud alkalinity, and promotion of phytoplankton growth in the oceans, it has been suggested that direct air capture (DAC) poses the lowest risk to radical ecosystem alteration.4 Furthermore, the success at efficient, large-scale CO2 capture from air may provide a source of a clean syngas exploiting process concepts under development for (i) combined CO2 and H2O splitting5 or (ii) reverse water gas shifting of renewable H2 6 that compete with the biomass gasification for commercially viable production of renewable transportation fuels.7


The paper is rather detailed and involved, but it may be useful to look at the pictures to get a feel for it:





The caption:
Figure 1. Schematic diagram of the CLDB setup. The sections outlined by the (blue) dashed and (green) dash-dotted lines represent the gas/sorbate supply manifold and the closed-loop test-rig, respectively. The (red) dotted lines indicate the gas flow direction during the adsorption experiments.




The caption:
Figure 2. (a) Disassembled and (b) assembled sample holder with the gas flow direction indicated by the yellow arrows and main components as follows: (1) PTFE gasket, (2) sorbent bed, (3) coiled stainless steel tube, (4) thermocouple, (5) upper flange, (6) KF clamp, (7) lower flange.




The caption:
Figure 3. Schematic of the tracer study setup.





The caption:
Figure 4. Comparison between the experimental and calculated CO2 mole fractions at the outlet of the tank assuming CSTR flow pattern. The zoom-in plots in panels b and c indicate error bars determined by the accuracy of the IRGAout.


IRGA stands for infrared gas analysis. CSTR = continuous stirred-tank reactor



The caption:
Figure 5. CO2 equilibrium loadings measured in TGA and CLDB setup under T = 35 °C. The solid line represents the Toth adsorption isotherm (eq 13) fitted to the TGA-determined equilibrium loadings.





The caption:
Figure 6. Effect of gas flow rate on the (a) CO2 and (b) H2O uptake profiles obtained with 30 mg of the sorbent under Tads = 30 °C, xCO2,0 = 1000 ppm, and RHads,0 = 50%. Larger fluctuations seen in Figure 6b are attributed to the inherently larger noise in xH2O measured with the IRGA.




The caption:
Figure 7. Sorbent bed temperature profiles recorded during the
experiments compared in Figure





The caption:
Figure 8. Amine-functionalized NFCs with the particle diameters of (a) 10 mm, (b) 4−5 mm, and (c) 1−2 mm
.



The caption:
Figure 9. Effect of sorbent particle diameter on (a) CO2 and (b) H2O uptake profiles obtained with 69 mg of the sorbent under ṅ = 0.074 mol· min−1, Tads = 25 °C, xCO2,0 = 6000 ppm, and RHads,0 = 50%.




The caption:
Figure 10. Sorbent bed temperature profiles recorded during the experiments compared in Figure 9. Note: the temperature of the dp = 10 mm particle was recorded with the thermocouple inserted into the sorbent particle while the remaining temperature sets were recorded with the thermocouple placed between the sorbent particles




The caption:
Figure 11. Leakage induced-relative errors of (a) CO2 and (b) H2O uptakes. The gray areas indicate the range of interest where adsorption kinetics are extracted.


Some excerpts from the text:

2.4. Data Analysis. The species j has an instantaneous adsorption rate rj (t) represented by the time derivative of the mass specific sorbate molar loading qj (t)


with qj (t) calculated from the temporal gas-phase species balance



where nj(t) and msorb represent the instantaneous sorbate amount in the gas phase within the closed-loop and mass of sorbent, respectively. The sorbate amount present in the gasphase can be determined using the ideal gas law if the sorbate mole fraction xj and the system pressure P, volume V, and temperature T are all known. Assuming the CSTR flow pattern in the tank and the plug flow through the reminder of the loop, xj is assumed uniform throughout the entire closed-loop. However, the pressure and temperature both vary within the loop due to the pressure drop in pipes, gas compression by the pump, and the lack of temperature control outside of the tank. To account for these nonuniformities in P and T, the closedloop was divided in several compartments as described in section S5 of the SI to calculate nj(t) as



where R is the universal gas constant and subscript “i” designates different compartments involved in the analysis. Note that the calculations of nj(0) and nj,(t) do not account for the exact same compartments, because the sorbate mixture bypassed the sorbent bed before the adsorption (see SI)...


...and...

The mixing of the gas in the tank was assessed by imposing a continuous tracer input into the tank and then comparing the experimental CO2 tracer mole fractions at the outlet of the tank with those calculated based on the assumption that the gas in the tank was perfectly mixed (CSTR condition). As the experimentally observed uniformity of the gas temperature and pressure within the tank implied that



the tracer material balance for the CSTR condition, that is, assumption that the CO2 composition in the tank is uniform and equal to that at the tank outlet, reduces to





In eqs 4 and 5, ntank designates the total amount contained within the tank and subscripts “in” and “out” indicate the quantities at the inlet and the outlet of the tank, respectively.


From the conclusion:

This paper presents development of a closed-loop setup for dynamic CO2 and H2O coadsorption on amine-functionalized NFC under conditions relevant to direct air capture. The setup, based on a differential sorbent bed placed outside of a perfectly gas mixing tank, allows for measuring the coadsorption kinetics in the absence of external heat and mass transfer effects that are commonly encountered in thermogravimetric analyzers and packed-bed reactors...

...The setup presented in this work can be readily implemented to determine the adsorption kinetics on other sorbents developed for similar applications as well as kinetics of some gas−solid catalytic or noncatalytic reactions. The design and validation methodologies presented in this paper can serve as a reference for the development of batch experimental setups for measuring adsorption/reaction kinetics free of the intrusions by heat and mass transfer.


The turn of events surrounding climate change are depressing because, in my opinion, even many of the people who get remain hostile to the only viable solution which necessarily will involve nuclear energy, but also require huge advancements in chemical technology and chemical and materials science engineering.

I will be gone from this planet soon enough, and I do not really expect, at my age, that things will really get better, but if they do, the work performed and published here, and thousands of examples more like it, written by scientists working in relative obscurity and enduring some popular contempt, will lead the way.

That it exists makes me feel a little better.

Have a wonderful weekend.







When the worst President in US history was in office, a tall, lanky, fun guy lost a Senate election.

He ran because an insanely racist Supreme Court made rulings that tore the country apart.

He lost, relatively narrowly, to Steven Douglas, racist, because he held locally unpopular opinions, but his espousal of these opinions garnered national attention.

Two years later, he was elected President of the United States, replacing the man considered, at least until recently, to be the worst President in US history, James Buchanan.

I am, of course, referring to Abraham Lincoln, Senate loser in 1858, who came to the 1860 convention as everybody's second choice for President, with the exception of some party leaders in his home state, Illinois, where he was the first choice.

The rest is history.

Just saying...

In case you ever find yourself looking for a monograph on the physics of bubbles, here it is.

Some time ago in this space, I wrote about Lord Rayleigh, at the height of his fame pausing to write a paper about what happens when water boils in a kettle: I just stumbled into a very old paper by "Lord Rayleigh" contemplating water boiling in a pot.

Lately I've been wondering about the physics of bubbles, specifically an unusual case, the physics of a bubble containg metallic gases formed from one or two or more immiscible metals appearing in a viscous liquid phase of another metal. Three metals have extraordinarily long liquid ranges: Gallium, plutonium and neptunium, the boiling points of the latter two having not been subject to direct laboratory measurement but rather inferred by extrapolation of their vapor pressures. (A great deal of plutonium was vaporized in the planetary atmosphere in the late 1940's, all through the 1950's and through much of the early 1960's, with smaller amounts having been so vaporized in rarer cases thereafter: It's still here.)

In the case where we consider doing something practical about reversing currently observed degradation of the climate - not that popular opinion shows even a trace of interest in reality - this situation might be of extreme importance: In liquid plutonium (or liquid neptunium) actively undergoing fission several volatile or potentially volatile metal gases are formed as fission products, notably cesium, rubidium, strontium and barium, as well as several inert gases, xenon, krypton and in proliferation proof plutonium, considerable helium. All of these elements are insoluble in liquid plutonium. Although this same volatility represented the greatest risk associated with the events at Fukushima and Chernobyl - it is also certainly conceivable to technologically exploit this very same process to do certain things, which might well take too long to describe.

Anyway, it took me a long time to locate a general monograph focused specifically on bubble dynamics, but finally I found and obtained one. This is it: Acoustic Cavitation and Bubble Dynamics.

There's two whole sections on Rayleigh's work on bubbles. Here's an excerpt on section 2.1, "Rayleigh–Plesset Equation."

A typical cavitation bubble is filled with vapor and non-condensable gas such as air. The pressure inside a bubble is higher than the liquid pressure at the bubble wall due to surface tension [1, 2]. The surface tension (r) is the surface energy per unit area and is 7.275 10^(−2) (N/m) (= J/m^(2)) for pure water at 20 °C. For a spherical bubble with a radius R, the surface energy is 4σπR^2 because the surface area is 4πR^2...


The next section is on "Rayleigh collapse."

As an aside, my son had the grace to inform me that I've been mispronouncing Rayleigh's name my entire and overly long life by the way, as well as the pronunciation of Auger's name in "Auger electrons" since both scientists' work has relevance to his undergraduate research.

I appreciate that. I'm amazed no one ever corrected me on this score before, either because they assumed I was too stupid to correct or that they had pity on the fact that I was born in Brooklyn.

You may never have any interest in the physics of bubbles; most people don't, and I didn't for much of an overly long life, but in case you do, here's a shortcut to avoid spending as much time as I did to find a comprehensive monograph on the subject of bubbles.

Have a nice day tomorrow.


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