Category Archives: CounterCurrent

Proteins, Receptors and Some Chemistry of Fentanyl

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[Note: This is a much-updated revision of a previous post from March 24, 2023. I’ve brought in just a tiny bit of protein structure and how it relates to opioid receptors- but only slightly. I’m thinking of you, dear reader. I’ve succumbed to my compulsion to include chemistry tutorials in my posts.]

First, a lot of chemists could say a lot of things on this topic. This is what I have to say. This essay is not written for medicinal chemists or molecular biologists. They already know this stuff. This is for everyone else. Learning usually requires an expansion of your vocabulary and this is no different.

When it comes to illicit drug synthesis I’ve always been a bit of a Puritan. As an organic chemist I’ve always felt that it is morally indefensible and a waste of talent for a chemist to make or help make dangerous and illegal drugs. Putting potent, illegal drugs on the market is like leaving a hand grenade in a playground.

For myself and for many others, what is fascinating about drug molecules is how structural features on a drug molecule confer pharmacological effects on biological systems. The molecular-level effects are referred to as a structure/activity relationship, or SAR. The chemical structure of a drug molecule makes all of the difference in how a drug functions. Among the key features are water solubility, acidity/basicity, hydrogen bonding, resistance to metabolic degradation, and the manner in which charge is distributed on the drug molecule. As a reminder, in order for two molecules to react they must bump into one another in a particular way. And not just that, but bump into a particular spot oriented properly and with sufficient energy.

Drug molecules do not swim directly to the site they are intended to go. They must take a random walk through flowing, jostling biofluid molecules and a certain minimum dose must survive the ordeal before they are metabolized, excreted or both. Some pharmaceuticals, called “pro-drugs“, are constructed in a way that relies on the action of metabolic processes to change them into the active drug. This is because they have some kind of chemical vulnerability and must be whisked into the body in disguise. Many drugs are bind to blood proteins and may remain unavailable for their action.

What the protein can do depends in large part on the sequence of amino acids that it is comprised of and how it relaxes into a largish, kinked and contorted chain with helices and pleated sheets. A protein polymer is made of a chain of amino acids that can interact with other molecules or with itself. Some lengths of a protein may lie flat and be somewhat rigid while other lengths may coil into a helical form. A protein molecule made of these features can then bunch up into a wad of protein that holds a particular shape. Along the surface of this shape are bumps, folds and crevices. In these places, there may be exposed amino acids that can attract acidic or positively charged parts of a molecule. Other spots may attract basic features like nitrogen with its lone pair of electrons. Still other places will attract molecular features with poor water solubility or just low polarity.

Drugs are used to activate or inactivate the function of a protein. Living things use proteins in several ways. In the case of drug action, proteins are large chemical structures that can make or break chemical bonds. proteins that do this can do it catalytically, that is, one enzyme molecule can perform its function repeatedly. That’s not all. There are features along the length of a folded enzyme chain that can attract, bind and even deform a molecule that is bound to it. In doing so, a chemical transformation can occur at physiological temperatures that might otherwise occur only under more chemically forcing conditions. This ability of enzymes is crucial to life itself.

Another function of proteins is the ability to change their shape to open or block the passage of smaller ions and molecules through it. The cell walls in our body consist of a double layer of fatty, detergent-like molecules that are water repelling on one side and water attracting, or ‘hydrophilic’, on the other. The water repelling, ‘hydrophobic’ side consists of a long chain of 2 or 3 hydrocarbon chains that comingle with one another.

In order for a drug to function it must bump into the target biomolecule like an enzyme (protein) and at a particular location on the enzyme. Some drugs may remain unchanged and just spend a lot of time bound to the active site of an enzyme, preventing the intended biomolecule from doing so. Others may permanently bind to a protein or other molecule, thereby blocking it from doing its job for the life of the enzyme. And others, like aspirin, may leave behind a fragment of itself permanently blocking the active site of an enzyme. Some drugs prevent a protein or enzyme from working and are called antagonists. Others may activate it and are called agonists. What you aim for depends on the system you are trying to manipulate.

A dip into proteins

An atom, ion or molecule that binds with a metal or a protein is called a “ligand“. A ligand, pronounced ‘LIGG und’ by organikkers and inorganikkers, or ‘LYE gand‘ by waterchemists biochemists, can connect with a protein through one or more attachment points. The greater the number and strength of the attachment point(s), the more time the ligand will spend being attached. A ligand may even become permanently attached. Ligands purposely or externally provided for a desired outcome are considered as “drugs”. Ligands that cause an undesired outcome may be referred to as toxic. Not all ligands are aimed at human proteins, however, such as the beta-lactam antibiotics which bind with certain bacterial enzymes. This is a fascinating topic all by itself, but it is left as an exercise for the dear reader.

Ligands or drugs can have specific structural features that are associated with its activity or potency. This assembly of molecular features on the ligand is called a “pharmacophore“. An enzyme will have small region on its surface that can accommodate the “docking” of a ligand with the right shape and polarity

Source: Wikipedia. This image is from x-ray data showing a ligand snugly fitting into a pocket on a protein. Crystal structure of W741L mutant androgen receptor ligand-binding domain and (R)-bicalutamide complex. An example of a protein–ligand complex.

In the image above, a close look will show a drug molecule sitting in a space that is complementary to its shape and polarity. If it turns out that this space is where the normal biological ligand docks in order for the enzyme to do something to or with it, then the enzyme behavior has been altered. The drug molecule being bound by the enzyme blocks the site that is normally occupied by the biological ligand. The biological ligand may enter the site to be chemically altered, or it may be the natural signaling agent that activates or deactivates the enzyme. The activation/deactivation may be permanent or not.

Another possibility for ligand-type activity is that of a cofactor. When the cofactor docks to an enzyme, the shape of the enzyme changes -a common effect- and another docking site is activated, enabling the enzyme to function. Some cofactors are vitamins or are made from vitamins.

The amino acid chain making up the enzyme is folded up in a particular way depending on the amino acid sequence. The overall shape of the enzyme consists of ridges, bulges, clefts and can also include a hole straight through the structure. Each of the 20 amino acids available is unique by way of its particular kind of chemical functional groups that are attached. If we imagine the exterior ‘surface’ of the protein, the amino acid chain twists and turns giving a lumpy surface topography. The different amino acids with their unique attached side-groups can jut out from the chain and be accessible to external molecules.

Different substances that share these features may comprise a family of substances having similar activity. In the case of opioids like fentanyl, this active site is referred to as an “opioid receptor“. There are a several variants of opioid receptors distributed throughout the human brain.

Opioid receptors are transmembrane proteins. They sit immobilized within the cell membrane with their external receptor protuberances gently swaying in the warm biofluid currents. They lie in wait for a shapely substate to happen by and nestle into its special cleft and be rewarded with a small release of Gibbs Energy.

The lipid bilayer of a cell membrane, comprising comingling long-chain hydrocarbon tails, is very hydrophobic (water repelling). Transmembrane proteins are compatible (likes dissolve likes) with that environment and can exist imbedded within the cell membrane. In this position, with access to both interior and exterior sides of the membrane, the protein is set up to be a receptor. A receptor is a protein that by virtue of its shape and polarity can recognize complementary shapes and polarities of a specific range of signaling molecules such as a hormone and transmit or release a chemical signal to the other side of the membrane.

Source: Wikipedia. The enzymes above are called transmembrane proteins. The opioid receptors are of this variety.
Source: Wikipedia. Complementary shapes. This illustrates ‘recognition’ of opioids by opioid receptors. Different but similar shapes can also be complementary but with varying degrees of affinity. Close resemblance in shape allows drugs to function.

End biochem section

According to the DEA, fentanyl is the most serious drug threat the US has ever faced. In the 12 months ending January, 2022, there were 107,375 deaths from drug overdoses and poisonings. Of those, 67 % involved synthetic opioids like fentanyl.

Fentanyl is not found in nature. It is made in a reaction vessel or a bucket by a person. It is totally synthetic in origin and is prepared from other manufactured substances. The molecule is relatively simple and there are many places on it where new functional groups can be attached to produce designer analogs. Due to its startlingly high potency, a large number of doses can be made in fairly small batch equipment.

The explosion of fentanyl use is mind boggling. Drug cartels have taken to producing it themselves for greater profit and a more secure supply chain. The common syntheses are fairly simple, high yielding and, in the case of fentanyl, there are no stereochemical issues other than the atropisomerism of the amide bond. As far as purification goes, this isomerism is difficult to control and it is hard to believe that it is considered a problem by the “cooks” who make it.

A quick search of Google failed to bubble up information on what chemical form of illegal fentanyl commonly shows up on the street, whether as a free-base form or a salt. Like most amines, the free-base could be salted out of a reaction mixture by addition of an acid to a solution of free-base fentanyl in an organic solvent to produce the insoluble salt crystals. This solid material is then recovered by filtration. This is a common method of recovering amines from a reaction mixture.

It is worth looking at a synthesis of fentanyl to see what kind of chemistry is performed (see below). There is nothing remarkable about this synthesis- it’s just an example. A key raw material is the 4-piperidone hydrochloride on the upper left of the scheme. It is a piperidine derivative which is a feature of many drug substances. This one has 2 functionalities– the nitrogen and the C=O at the opposite end of the ring. Connections will be made at each end as the synthesis proceeds. The hydrochloride feature results from how the manufacturer chose to sell the product. Ammonium salts are frequently more shelf stable than the free amine.

The first step in the process below combines 4-piperidone hydrochloride with phenethyl bromide in the presence of cesium carbonate in solvent acetonitrile. In this transformation the nitrogen displaces the bromide to form a C-N bond connecting the fragments. Cesium carbonate is a base that scavenges acid protons. According to Wikipedia, cesium carbonate has a higher solubility in organic solvents than do the sodium or potassium analogs. Cesium carbonate is commonly used when a base stronger than sodium carbonate is needed. In order for the reaction to go forward, the HCl must be neutralized to liberate the free base. It is hard to imagine that the folks doing an illegal preparation are using a cesium base due to higher cost. The displacement of the bromide by nitrogen releases hydrobromic acid as well which must be removed from the mixture. Bromide is chosen because it is a good leaving-group. para-Toluenesulfonate, or tosylate, has been used as well.

Next, aniline must be added to the piperidone ring where the C=O is located. We have to end up with a single C-N bond connection from the aniline nitrogen to the C=O double bond then remove the oxygen and replace it with a hydrogen atom. Aniline is quite toxic and volatile with an LD50 of 195 mg/kg (dog, oral). It stinks too. This sequence is referred to as a “reductive amination“, meaning that the oxygen is replaced by single bonds to nitrogen and hydrogen. Adding hydrogen to a molecule is referred to as a reduction. The authors of the work commented that of three hydrogen donors tried, sodium triacetoxyborohydride gave the best yields. These borohydrides donate hydrogen as the negatively charged hydride, H:–.

Acetonitrile is a polar aprotic solvent that allows enough solubility to the reagents and intermediates so as to help the reaction along. Reductive amination classically proceeds through a C=N (imine) intermediate which then undergoes a hydrogen reduction of the bond to give the amine product.

The two-nitrogen intermediate is then fitted with a 3-carbon fragment bearing a C=O to the aniline nitrogen connected to the benzene ring. With this transformation, the amine nitrogen becomes an amide nitrogen. The fragment added is called propanoyl chloride (pro-PAN-oh-ill KLOR-ide) and involves the displacement of the chloride with the nitrogen producing hydrochloric acid. The purpose of the diisopropylethylamine base is to serve as an acid scavenger. The solvent was dichloromethane which is not uncommon for this kind of reaction. It has a low boiling point for easy removal by distillation and a slight polarity for dissolving substances that are somewhat polar. It is also inert to the reaction conditions.

It takes a high level of education, training and resources to design and perfect a process like the one above. However, it can be executed by most people after a bit of training. You don’t have to be a chemist to follow the procedure. The trick will be to avoid poisoning yourself from aniline or fentanyl exposure in the process.

However illegal fentanyl is made, the raw materials going into it must combine to give one unique final product. There are not an infinite number of pathways to fentanyl. However, structural variations of the raw materials could be chosen using the same basic reaction conditions to produce a spectrum of designer analogs. If specific molecules are outlawed, analogs can readily pop up to skirt regulations.

The people who make illicit fentanyl are sourcing the raw materials from somewhere. Unlike heroin, there are no natural substances in the manufacture of fentanyl. Heroin is just plant-based morphine that has been acetylated. Acetic anhydride is the choice commercial reagent for this. The acetic anhydride supply chain can be traced. Fentanyl, however, requires a supply chain for numerous fine chemicals. In the US, many substances are flagged by suppliers in a way that could cause the authorities to investigate the buyer. Furthermore, US commercial suppliers often could do a Dun & Bradstreet credit check on you to gauge your suitability as a customer. Commercial chemical suppliers will not ship to a residential address or PO box. So it takes a bit of business structure to get chemicals sent from established chemical suppliers to your address.

The way to avoid this hassle is to import from somewhere like Asia. Given the high potency of fentanyl, the mass of raw materials in a shipment could be very low. Most organic chemicals are whitish or colorless and can be mislabeled. The lower the molecular weight of a substance, the lower the mass that will be needed for the process. There are no high MW reagents in the scheme above.

Herein lies the problem with fentanyl. It requires raw materials that have legitimate uses in the chemical/pharmaceutical industry and these substances can received by unscrupulous operators who can repackage and divert shipments to the bad guys in countries along the Pacific coast of the Americas. It is just simple smuggling.

The estimated lethal dose of fentanyl for humans is 2 milligrams. According to one source, “The recommended serum concentration for analgesia is 1–2 ng/ml and for anesthesia it is 10–20 ng/ml. Blood concentrations of approximately 7 ng/ml or greater have been associated with fatalities where poly-substance use was involved.” Overdosing with fentanyl is reportedly treatable with naloxone. But this is only effective if your unconscious body is found by a sympathetic bystander and help is called in promptly. This is a very slender reed from which to hang your life.

It is left to the reader to look further into the pharmacology and therapeutic window details fentanyl. Suffice it to say that dosing yourself with illicit opioids is a stupidly risky business. The illegal opioid risk is multiplied by other additives or the possible presence of designer analogs which may be 10 to 100 times more potent. End-use safety is not a priority of those who make and distribute these opioids.

Given the estimated 2 mg lethal dosage, fentanyl should be regarded as a highly toxic substance. As long as there is demand for potent opioid substances, someone will provide it. When the oxycodone supply tightened recently, heroin demand rose. It’s a deadly whack-a-mole situation. The only answer is reduced demand.

Machismo and Violence

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The present situation is one whereby a large swath of the population, including K-12 students, are being exposed to an increased risk of bloody, violent death sustained by those who fetishize firearms. Whatever you may think of the 2nd Amendment to the US Constitution, the fact is that we are prioritizing an originalist interpretation over the lives of school children. We are allowing children to be sacrificed on the alter of the 2nd Amendment in order to satisfy people who idolize the idea of boundless access to metal tubes that discharge high energy bits of metal. We are not officially at war defending our borders in the US nor are we on the verge of a civil war. By far, most guns are not used to hunt. Most Americans lead peaceful lives in their neighborhoods without the need to shoot at people.

The very notion that the US government is going to wrench guns away from citizens in one of the most heavily armed democratic countries in the world is the fever dream of a fool. Any full-scale attempt to do this would lead to armed rebellion and the collapse of the USA as a democratic republic. Widespread gun confiscation is not politically feasible today or in the foreseeable future.

We must tone down and be less tolerant of the image of inflated machismo that guns confer to their users. Both in real life and in entertainment, gunplay is used to resolve conflict. By far, most gun owners do not commit violent acts with their guns. While they should not be penalized for the crimes committed by others, accepted mechanisms like driver’s and pilot’s licenses are a form of limitation and standardization that could be applied to access to firearms. But this reliably produces hysteria among the armed public. Like everything else in society, a few people have to ruin it for the rest of us.

The basic utility of a gun is to deliver crippling or fatal kinetic energy, or the threat of it, from a safe distance. The need for guns for peacekeeping use will last as long as there is dangerous criminality. What the US is presently suffering from is the use of rapid-fire, high-energy projectiles from guns designed to hit as many targets as possible in the shortest time. Man killers.

Sidebar

I took the hunter’s safety course sponsored by the NRA at the age of 9. The truth is that firing a gun is both fun and stimulating. I recall stealthily walking along a muddy creek in the Iowa countryside with a bolt action 0.22 caliber rifle desperately looking for some reason the fire the gun. I spotted fish, turtles and birds but something held me back from shooting at them except for once a few years later. With a BB gun I shot a sparrow perched on a small twig of an elm tree. The bird rotated backwards, still gripping the twig, and hung upside down for a minute or two. Then it released and dropped into an irrigation ditch with a small splash.

I was immediately gripped with regret and sorrow for what I had just done. I had just killed a random sparrow for utterly no reason than to see what happens. Even as a teenager I could see that this was a senseless action. I am sorry for killing the sparrow to this very day and, except for a few mice and bugs, I have never killed wildlife since.

Back to the essay

The point of the story above is that, for me, being in possession of a firearm could sometimes produce a strong urge to fire it. I’m confident that there are others who have felt the same way. The healthy release is to do target practice. Some people enjoy hunting. I do not indulge in this because I prefer the flavor of beef, pork and fish which, conveniently, are already butchered.

Male characteristics can have both good and bad attributes. A measure of focused male aggressiveness, ambition and territoriality can be beneficial for the wellbeing of loved ones and the community. Brute strength can be quite useful in providing for a family. Male rage, however, can be very destructive wherever it is directed, as we all know. A firearm or other weapon is a force multiplier for a raging male. Recent mass killings prove the point. Firearms provide the ability to kill or wound from a safe distance and the value of this is lost on no one.

It is hard to imagine that some restraint in the use of firearms without addressing the cultural and natural phenomenon of male aggression can be successful. We are saturated with violence in entertainment, on the streets and in the news. As long as we seek entertainment violence, show business will anxiously provide it.

I’m neither a Quaker nor a pacifist but I do admire their sincere dedication to non-violence. We need many early adopters of non-violence with considerable social standing and a non-violence vibe across the whole country. Destructive male behavior can be tamed to a great extent, but it has to start early and be immersed in non-violent surroundings. Where is the sign that Americans can summon the discipline to do it. I’m not seeing it.

Lamentations on Science Infotainment Rev 2.

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Note: This post appeared May 15, 2007, as “Infotainment, Chemistry, and Apostasy“. I have pulled it up through the mists of time for another go and with a few edits.

In the normal course of things I used to give school chemistry talks or demonstrations a couple of times per year and until recently, I had been giving star talks at a local observatory more frequently.  The demographic is typically K-12, with most of the audience being grades 3-8.  From my grad student days through my time in the saddle as a prof, I was deeply committed to spreading the gospel of orbitals, electronegativity, and the periodic table. I was convinced that it was important for everyone to have an appreciation of the chemical sciences.  I was a purist who knew in his bones that if only more people were “scientific”, if greater numbers of citizens had a more mechanistic understanding of the intermeshing great world systems, the world could somehow be a better place. 

In regard to this ideology that everyone should know something about chemistry, I now fear that I am apostate.  I’m a former believer.  What has changed is an updated viewpoint based on experience.  

Let me make clear what science is not. It is not a massive ivory tower that is jealously guarded ajd intended to be impenetrable by mortal folk. Big science requires big funding and organizational support, so big administrative structure forms around it. At its core, science is concerned with learning how the universe works by observation, constructing a good first guess (theory) on what is happening, measurement (conducting quantitative experiments), analysis (quantitative thinking), documentation and communication. The common understanding is that a scientist is someone who has been educated and employed to do these activities. However, anyone who conducts a study of how some phenomenon happens is doing science whether for pay or not.

What science has learned is that the universe is quite mechanistic in how it works. So much so that it can be described by or represented with math. At the fundamental level of ions, atoms and molecules, constraints exist on how systems can interact and how energy is transferred around. At the nanometer-scale, quantum mechanical theory has provided structure to the submicroscopic universe.

Chemical knowledge is highly “vertical” in its structure.  Students take foundational coursework as a prerequisite for higher level classes.  Many of the deeper insights require a good bit of background, so we start at the conceptual trailhead and work our way into the forest. But in our effort to reach out to the public, or in our effort to protect a student’s self-esteem, we compress the vertical structure into a kind of conceptual pancake.  True learning, the kind that changes your approach to life, requires Struggle.

What I found in my public outreach talks on science- chemistry or astronomy- was the public’s expectation of entertainment. Some call it “Infotainment”.  I am all in favor of presentations that are compelling, entertaining, and informative.  But in our haste to avoid boredom, we may oversimplify or skip fascinating phenomena altogether. After all, we want people to walk out the door afterwards wanting more. We want science to be accessible to everyone, but without all the study.

But I would argue that this is the wrong approach to science.  Yes, we want to answer questions.  But the better trick is to pose good questions.  The best questions lead to the best answers. People (or students) should walk out the door afterwards scratching their heads with more questions.  Science properly introduced, should cause people to start their own journey of discovery. Ideally, we want to jump-start students to follow their curiosity and integrate concepts into their thinking, not just compile a larger collection of fun facts. 

But here is the rub. A lot of folks just aren’t very curious, generally.  As they sit there in the audience, the presentation washes over them like some episode of “Friends”.  I suspect that a lack of interest in science is often just part of a larger lack of interest in novelty.  It is the lack of willingness to struggle with difficult concepts.  But that is OK.  Not everyone has to be interested in science.

Am I against public outreach efforts in science?  Absolutely not.  But the expectation that everyone will respond positively to the wonders of the universe is faulty.  It is an unrealistic expectation on the 80 % [a guess] of other students who have no interest in it. I’m always anxious to help those who are interested.  It’s critical that students interested in science find a mentor or access to opportunity.  But, please God, spare me from that bus load of 7th graders on a field trip. 

What we need more than flashier PowerPoint presentations or a more compelling software experience is lab experience.  Students need the opportunity to use their hands beyond mere tapping on keyboards- they need to fabricate or synthesize. You know, build or measure stuff. 

It is getting more difficult for kids to go into the garage and build things or tear things apart.  Electronic devices across the board are increasingly single component microelectronics.  It is ever harder to tear apart some kind of widget and figure out how it works.  When you manage to crack open the case what you find is some kind of green circuit board festooned with tiny components. 

And speaking of electronics or electricity, I find it odd that in a time when electric devices have long been everywhere in our lives, that so FEW people know even the first thing about electricity. I instruct an electrostatic safety class in industry and have discovered that so very, very few people have been exposed to the basics of electricity by graduation. I spend most of the course time covering elementary electrostatic concepts along with the fire triangle so the adult learners can hopefully recognize novel situations where static electric discharge can be expected. Of course, we engineer away electrostatic discharge hazards to the greatest extent possible. But if there is a hole, somebody will step in it. It’s best they recognize it before stepping into it.

The widespread educational emphasis on information technology rather than mechanical skills ignores the fact that most learners still need to handle things. There is a big, big world beyond the screen. A person will take advantage of their mechanical skills throughout their life, not just at work. Hands on experience is invaluable, in this case with electricity. Computer skills can almost always be acquired quickly. But understanding mechanical, electrical and chemical systems need hands-on experience.

Technological Triumphalism

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“Technological triumphalism” is a term that surfaces infrequently, encapsulating the belief in our capacity to resolve almost any issue through the innovative use of technology. While technological progress has led to countless pivotal breakthroughs, such as antibiotics and the transistor, it has also given rise to means that magnify age-old human tendencies towards negative behaviors. As our tools and methods evolve with technological advancements, so too do our desires and avarice, often intensified by the fresh opportunities new technologies present.

As an example of technology bursting on the scene producing both good and bad consequences, consider the Haber-Bosch process for the industrial manufacture of ammonia. An industrial feedstock like ammonia can split into several streams. On the plus side, cheap and available liquid or gaseous ammonia for fertilizing crops was a boon for mankind in terms of increased food production. Also, the combination of ammonia and nitric acid leads to the production of the solid fertilizer ammonium nitrate.

Another and wholly different product stream involving the oxidation of ammonia (Ostwald Process) is nitric acid production, HNO3. It is required for the manufacture of industrial intermediates, high explosive nitroaromatics like TNT, picric acid, nitroesters like nitroglycerine and even more powerful explosives. Explosives are neither inherently good or bad, their merits depend on how they are used. When used for construction or mining, explosives are a positive force in civilization. However, they cast a long dark shadow when used to destroy and kill.

Fritz Haber

A good example of unanticipated consequences of a technology uptick is found in the story of the German chemist Fritz Haber. Haber won the 1918 Nobel Prize for Chemistry for the invention of the Haber-Bosch synthesis of ammonia. It is estimated the 1/3 of present global food production relies on the use of ammonia from the Haber-Bosch or similar processes. Haber has been widely praised for his part in the invention of catalytic ammonia production using atmospheric nitrogen. These are important developments, but … [Wikipedia]

As a German nationalist, Haber was also known for his considerable contributions to German chemical warfare through WWII. Haber was responsible for the production of Zyklon A and Zyklon B.

It is claimed that neither Fritz Haber nor Carl Bosch were fans of National Socialism in Germany in the 1930’s. Haber claims to have done his WWI gas warfare work for Kaiser Wilhelm as a German patriot. Intimidated by German laws aimed at Jews and Jewish colleagues, Haber (a Jew converted to Catholicism) left Germany in late 1933 for a position as director of what is now the Weizman Institute in what was at that time Mandatory Palestine. He died while enroute in the city of Basel, Switzerland, at age 65.

Chemical warfare in WWI began with an idea from volunteer driver and physical chemist Walther Nernst who suggested in 1914 the release of tear gas at the front. This was observed by Haber who later suggested chlorine gas be used instead because of its density. Haber personally supervised Germany’s first release of chlorine gas at the Second Battle of Ypres in WWI. Supervising the installation of the 5730 tanks of chlorine were chemist Fritz Haber, chemist Otto Hahn, physicist James Franck and physicist Gustav Herz. Of the 5 scientists mentioned above, Nernst included, all would receive a Nobel Prize in their lifetimes.

‘Haber defended gas warfare against accusations that it was inhumane, saying that death was death, by whatever means it was inflicted and referred to history: “The disapproval that the knight had for the man with the firearm is repeated in the soldier who shoots with steel bullets towards the man who confronts him with chemical weapons. […] The gas weapons are not at all more cruel than the flying iron pieces; on the contrary, the fraction of fatal gas diseases is comparatively smaller, the mutilations are missing”.’ Source: Wikipedia.

The double-edged sword of ammonia. The military benefits apply to both offensive and defensive use. Graphics by Arnold Ziffel.

The Future

Ask yourself this- will your descendants in the year 2124 share in the creature comforts coming from the extravagant use of resources as we have? Doesn’t the word “sustainability” include the needs of 4-5 generations down the line?

There are wants and there are needs. For many of us in the 21st century, most our needs in the US are more than satisfied along with surplus income to satisfy many of our wants. Will our descendants a century from now even have enough resources to meet their needs after our continuing wanton and extravagant consumption of resources of the last 150 years?

Our technology stemming from the earth’s economically attainable resources has done much to soften the jagged edges from nature’s continual efforts kill us. After each wave of nature’s threats to life itself, survivors get back up only to face yet more natural disasters, starvation and disease. This is where someone usually offers the phrase “survival of the fittest”, though I would add ” … and the lucky“.

What will descendants in 100 or 200 years require to fend off the harshness of nature and our fellow man? Pharmaceuticals? Medical science? Fuels for heat and transportation? Will citizens in the 22nd century have enough helium for the operation of magnetic resonance imagers or quantum computers? Will there be enough economic raw materials for batteries? Will there be operable infrastructure for electric power generation and distribution? Lots of questions that are easy to ask but hard to answer.

If you are immune from concern for future generations, then this essay is a waste of your time.

Come to think about it, does anyone worry this far in advance? The tiny piece of the future called “next year” is as much as most of us can handle. Is the world a much smaller place than it used to be or is the scale just better understood?

A plug for climate change

Even the sky is smaller than we think. At 18,000 feet the atmospheric pressure drops to half that at sea level. This means that half of the molecules in the atmosphere are at or below 18,000 feet. This altitude, the 500 millibar line, isn’t so far away from the surface. From the 58 Fourteeners in Colorado, it is only 4000 ft up. Not that far. The breathable, inhabitable atmosphere is actually quite thin. The Earth’s atmosphere tapers off into the vacuum of space over say 100 km, the Kármán line. While this is more of an arbitrary designation than a physical boundary between the atmosphere and space, the bulk of the atmosphere is well below this altitude. With this in mind, perhaps it seems more plausible that humans could adversely affect the atmosphere.

The lowest distinct layer of the atmosphere is the troposphere beginning as the planetary boundary layer. This is where most weather happens. In the troposphere, the atmospheric temperature begins to drop by 9.8 °C per kilometer or 5.8 oF per 1000 ft of altitude. This is called the dry adiabatic lapse rate.

With increasing altitude, the atmospheric temperature gradient decreases to about 2 oC per kilometer at ~30,000 ft in the mid-latitudes where the tropopause is found. The tropopause is where the lapse rate reaches a minimum then the temperature remains relatively constant with altitude. This is the stratosphere.

Over the last 200 years in the West at least, advances in medicine, electrical devices, motor vehicles, aerospace, nuclear energy, agriculture and warfare have contributed to what we both enjoy and despise in contemporary civilization. The evolving mastery of energy, chemistry and machines has replaced a great deal of sudden death, suffering and drudgery that was “normal” with a longer, healthier life free of many of the harmful and selective pressures of nature. Let’s be clear though, relieving people of drudgery can also mean that they may be involuntarily removed from their livelihoods. It is quintessentially American to sing high praises to capitalism. It is even regarded as an essential element of patriotism by some. On the interwebs capitalism is defined as below-

Capitalism is an economic system based on the private ownership of the means of production and their operation for profit.

As I began this post I was going to cynically suggest that capitalism is like a penis- it has no brain. It only knows that it wants more. Well, wanting and acquiring more are brain functions, after all. Many questions stand out, but I’m asking this one today. How fully should essential resources be subject to raw capital markets? It has been said half in jest that capitalism is the worst economic system around, except for all of the others.

I begin with the assumption that it is wise that certain resources should be conserved. Should it necessarily be that a laissez faire approach be the highest and only path available? Must it necessarily be that, for the greater good, access to essential resources be controlled by those with the greatest wealth? And, who says that “the greater good” is everybody’s problem? People are naturally acquisitive, some much more than others. People naturally seek control of what they perceive as valuable. These attributes are part of what makes up greed.

Obvious stuff, right?

The narrow point I’d like to suggest is that laissez faire may not be fundamentally equipped to plan for the conservation and wise allocation of certain resources, at least as it is currently practiced in the US. Businesses can conserve scarce resources if they want by choosing and staying with high prices, thereby reducing consumption. However, this is not in the DNA of business leaders. The long-held metrics of good business leadership rest on the pillar of growth in market share and margins. Profitable growth is an important indicator of successful management and a key performance indicator for management.

Firstly, a broader adoption of resource conservation ideals is necessary. Previous generations have indeed practiced it, with the U.S. national park system serving as a notable example. However, the scarcity of elements like Helium, Neodymium, Dysprosium, and Indium, which are vital to industry and modern life, raises concerns. The reliance of Magnetic Resonance Imaging (MRI) operators on liquid helium for their superconducting magnets poses the question of whether such critical resources should be subject to the whims of unregulated laissez-faire capitalism. While some MRI operators utilize helium recovery systems, not all do, leading to further debate on whether the use of helium for party balloons should be permitted to continue, given its wasteful nature.

Ever since the European settlement of North America began, people have been staking off claims for all sorts of natural resources. Crop farmland, minerals, land for grazing, rights to water, oil and gas, patents, etc. Farmers in America as a rule care about conserving the viability of their topsoil and have in the past acted as a group to maintain it in good condition. But, agribusiness keeps making products available to maximize crop yields, forcing farmers to walk a narrower line with soil conservation. Soil amendments can be precisely engineered with micronutrients, nitrogen and phosphate fertilizers to reconstitute the soil to compensate for higher yields. Herbicides and pesticides are designed to control a wide variety of weeds, insect and nematode pests. Equipment manufacturers have pitched in with efficient, though expensive, machinery to help extract the last possible dollars’ worth of yield. Still other improvements are in the form of genetically modified organism (GMO) crops that have desirable traits allowing them to withstand herbicides (e.g., Roundup), drought or a variety of insect, bacterial, or fungal blights. The wrench in the gears here is that the merits of GMO have not been universally accepted.

Livestock production is an advanced technology using detailed knowledge of animal biology. It includes animal husbandry, nutrition, medicines, meat production, wool, dairy, gelatin, fats and oils, and pet food production. There has been no small amount of pushback on GMO-based foods in these areas, though. I don’t watch this in detail so I won’t comment on GMO.

The point of the above paragraphs is to highlight a particular trait of modern humans- we are demons for maximizing profits. It comes to us as naturally as falling down. And maximizing profits usually means that we maximize throughput and sales with ever greater economies of scale. Industry not only scales to meet current demand, but scales to meet greater future demand.

Extracting a resource to its exhaustion has been prevalent in history. The question is, is it inevitable or can or should it be throttled back?

Essentially everyone will likely have descendants living 100 years from now. Won’t they want the rich spread of comforts and consumer goods that we enjoy today? Today we are producing consumer goods that are not made for efficient economic resource recovery. Batteries of all sorts are complex in their construction and composition. Spent batteries may have residual charge left in them and have chemically hazardous components like lithium metal. New sources of lithium are opening up in various places in the world, but it is still a nonrenewable and scarce resource. This applies to cobalt as well.

Helium is another nonrenewable and scarce resource that in the US comes from a select few enriched natural gas wells. At present we have an ever-increasing volume of liquid helium consumption in superconducting magnets across the country that need to remain topped off. This helium is used in all of the many superconducting magnetic resonance imagers (MRI) and nuclear magnetic resonance (NMR) spectrometers in operation worldwide. Quantum computing will also consume considerable liquid helium as it scales up since temperatures below the helium boiling point of 4.22 Kelvin are required.

As suggested above, today’s MR imagers can be equipped with helium boil off prevention recovery devices that recondense helium venting out of the cryostat and direct it back into a reservoir. One company claims that their cold head condensers are so efficient that users do not even have to top off with helium for 7-10 years. That is a good thing. Hopefully it is affordable for most consumers of MRI liquid helium.

In the history of mining in the US and elsewhere, it has been the practice of mine owners to maximize the “recovery” of ore when prices are high. Recovery always proceeds to the exhaustion of the economical ore or the exhaustion of financial backing of the mining company. Uneconomical ore will remain in the ground, possibly for recovery when prices are more favorable. It is much the same for oil and gas. As with everything, investors want to get in and get out quickly with the maximum return and minimum risk. They don’t want their investment dollars to sit in the ground waiting for the distant future in order to satisfy some pointy headed futurist and their concern for future generations.

It is not normally in the nature of for-profit corporate C-suite executives to aim for resource conservation. People answerable to a board of directors have a fiduciary responsibility to maximize wealth generation for the shareholders. The world of industry is the world of growth. The world of “let’s make enough to get by” is not the world of people who rise to the C-suite. Unfortunate but true.

What is needed in today’s world is the ability to conserve resources for our descendants. It requires caring for the future along with a good deal of self-control. Conservation means recycling and reduced consumption of goods. But it also means tempering expectations of wealth generation, especially for those who aim for large scale production. While large scale production yields the economies of scale, it nevertheless means large scale consumption as well, In reality, this is contrary to the way most capitalism is currently practiced around the world.

Sustainability

The libertarian ideal of applying market control to everything is alleged to be sustainable because in appealing to everyone’s self-interest, future economic security is in everyone’s interest. If high consumption of scarce resources is not in our self-interest, then will the market find a way to temper it? As prices rise in response to scarcity, consumption will drop. ECON-101 right? Well, what isn’t mentioned is that it’s today’s self-interest. What about the availability of scarce resources for future generations? Will the market provide for that? What does “sustainability” really mean? Does it mean that today’s high consumption is sustained, or does it mean resource conservation?

Is the goal of energy sustainability to maintain the present cost of consumption but through alternative means? Reduced consumption will occur when prices get high enough. As the cost of necessities rises, the cash available for the discretionary articles will dry up. How much of the economy is built on non-essential, discretionary goods and services? The question is, does diminished consumption have to be an economic hard landing or can it be softened a bit?

Some chemical elements

Here is where we transition into some chemistry. Our transition into a more electric world requires the use of certain chemical elements that may be unfamiliar to many. Certain elements are critical such as copper, aluminum, steel, silicon, germanium, gallium, neodymium, lithium, indium, boron and some others. And each element requires industrial plants and mining to produce them. Mining and refining generally use large quantities of electric power and water. Most all of the equipment in the mines and industry rely on steel machinery which itself requires a cascade of resources to produce.

As of the date of this writing, we are already down the timeline by many decades as far as the R&D into alternative electrification. What we are faced with is the need for a rapid and very large scaling-up of renewable electric power generation, transmission and storage for the anticipated growth in power consumption for electric vehicles.

Price elasticity is where an increase in price fails to result in a drop in demand. Necessary or highly desirable goods and services may not drop in demand if the price increases at least to some level. As with the price of gasoline, people will grumble endlessly about gas prices as they stand there filling their tanks with expensive gasoline or diesel. Conservation of resources has to overcome the phenomenon of price elasticity in order to make a dent without shortages.

A meaningful and greater conservation of resources will require that people be satisfied with lesser quantities of many things. In history, people have faced a greatly diminished supply of many things, but not by choice. Economic depression, war and famine have imposed reduced consumption on whole populations and often for many years. When the cause is released, people naturally return to consumption as high as they can afford.

The technological triumphalism reflex of civilization has allowed us to paint ourselves into a resource scarcity corner. We are reliant on new technology that itself is reliant on more mature technology.

Added 10/30/24.

The habit of relying on future technological breakthroughs to solve current problems is universally seen as a positive expression except for those culturally disconnected from modernism such as the Amish, etc. The problem arises when we blunder forward, oblivious to consequences of the technology. Unforeseen consequences are notably difficult to visualize early in development and may be interpreted by some as negativism.

In chemical manufacturing we are accustomed to a performing PHA- Process Hazard Analysis -when starting up a new process. In a PHA meeting we list all of the potential points of failure in the process equipment and then brainstorm every possible failure mode and possible links to other equipment. It usually takes most of a shift and it is essential that engineers and plant operators are present to lend their expertise. As potential failures are identified they are rated according to their likelihood and seriousness. Each entry that calls for a dated action item by persons responsible for solving the problem.

What the PHA also does is to alert those involved in designing processes of problems that may be general in nature and worth remembering for the next process.

Social Media- An invention gone bad?

Did the persons who introduced the various social media platforms in the early days consider the possible malevolent use and consequences of their online products? Was anything other than the rapid development of their platform and getting online as fast as possible even considered? Was there a devil’s advocate in the building at the time? Once money is invested in a business plan or invention, the desire to go to market becomes insurmountable.

If the question is “could trolls and other online troublemakers have been avoided from the beginning?”, then perhaps the early social media developers should have some accountability to those who download the app. If not, what should be the developer’s role in solving the problem of online trolling or fraud?

As with so many useful things in the marketplace that have a dark side, weapons for instance, doesn’t the user have some responsibility for proper use? Well, yes and no. Someone who knows about guns should have the responsibility for its use, that’s yes. Going very dark, what about leaving a loaded and chambered pistol on a playground. Is it reasonable to expose children to the danger from mishandling? Should they be expected to know what the loaded pistol could do? Clearly not.

The core of the issue seems to be the matter of when a seemingly innocuous invention is released for global use and is unexpectedly misused by some users. Is the developer responsible for damages resulting from the misuse? Can the developer be forced to harden their product to attenuate the abuse?

Could it be that clamping down on trolls on a given app will involve a reduction of clicks or eyeballs? Would advertisers overlook this or negotiate a lower price?

It is doubtful that anyone in 1975 was begging for a Facebook to come on the market. Dot matrix printers were a marvel then. Eventually, when available, Facebook would take the world by storm. Demand appeared when people became aware of it. Is it a triumphal bit of technology? Both were built to exploit existing telecommunications technology and data collection systems. Facebook is a system that converts views and clicks into money over the internet. Facebook is a product that delivers our eyeballs and data to advertisers. Similar to a newspaper or television. Fb is triumphal to advertisers and Meta.

Conclusion-

Is there really such a thing as general Technological Triumphalism? I’m beginning to think that it might exist only as squinted at from 50,000 feet. In the very early 20th century, physicians longed for a magic bullet to cure infections apart from the toxic mercurials then in use. They needed a Technological Triumph, and it arrived in pieces through experiments over time. Along came sulfa drugs, then penicillin and both of these were explored for more potent analogs. As medicinal chemistry advanced, entirely new classes of antibiotics were discovered. The lesson of penicillin coming from mold led to the exploration of microbial and fungal sources from all over the world, producing antibiotics affecting a variety of systems in gram (+) and gram (-) bacteria. Once an active candidate is discovered, it’s structure and stereochemistry are determined. Once the composition is known, modifications can be prepared to explore the efficacy of analogs and sort out the mechanism of its antibiotic properties.

Technological Triumphalism can be a philosophy that in its hazardous form can lead people to believe that if a technology goes surprisingly bad, certainly something can be invented to make it better. Fix one technology with another. The discovery of antibiotics was the result of answering a question that begged for a solution.

An example is the problem of CO2 in global climate change. Should we compensate for rising CO2 emissions by scrubbing the atmosphere or should we find a way to reduce emissions by driving fewer miles? The first is a technological solution and the other is more of a lifestyle change.

Limitations of Quantum Computing

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Note: First, let me make clear that I am not a computer scientist and while I’ve learned FORTRAN, BASIC and PASCAL in the early 1980’s followed by coursework in quantum chemistry in grad school- and somehow passed– the question of how quantum computation actually computes with qubits remains a mystery to me. Honestly, I’m weary of hearing about it. That said, I do continue to worry about the ever-increasing pressure on the liquid helium tit which quantum computing will definitely lock on to.

An interesting article came out in the current issue of Quantum Magazine giving some straight talk about how quantum computers might actually be used. All of us have been bombarded by breathless predictions of a wondrous future where we can find prime factors of stupidly large numbers and crack very secure cryptography.

Quantum chemistry is about orbiting electrons confined to particular regions of oddly shaped space around a positively charged nucleus, depending on their energy. That is a lifetime of study right there for me. I think I’ll stick to atoms and molecules.

Oh yes, in the early 80’s we used an IBM 360 and submitted our batch jobs as a stack of punch cards. Eventually we were allowed to use the DEC writer for BASIC programming. One sunshiny day an Apple 2 appeared in the chemistry department office. It had 16 K of memory, a green monitor and an external floppy disk drive. There were whispers that 32 and maybe even 64 K were on the horizon. Heady stuff.

The IT guys were surly then too.

Amassing Cannon Fodder is an Old Soviet Tactic

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After reading a biography of the Russian Marshal of the Soviet Union, Georgy Zhukov, it becomes apparent that there are parallels between Soviet tactics in WWII and those used in the Putin-Ukraine conflict. Beyond the deployment of similarly vintaged tanks and weaponry, General Zhukov was notorious for committing his forces to battle with little regard for casualties. Similarly, Putin’s military has been characterized by the use of inadequately trained and equipped conscripts. Additionally, it has been reported that Putin’s forces have positioned troops behind the front lines to prevent or even target any deserting or retreating frontline soldiers. Zhukov’s approach often involved rapidly advancing battalions and armor to the front with minimal planning, depending on the attrition of Nazi forces. This tactic was typically executed under Stalin’s direct orders, though sometimes initiated by Zhukov independently.

The conflict between Putin and Ukraine has evolved into a war of attrition. Initially, Putin thought he could swiftly deploy tanks and troops as he did in southern Ukraine in 2014, seizing territory through sheer intimidation. However, he miscalculated the armaments, determination and tenacity of the Ukrainian forces. Since 2014, tens of thousands of Ukrainian soldiers have received training from Western nations. By February 2022, they were significantly better prepared and less intimidated by Putin’s military. In conventional warfare, the Russian military turned out to be a paper tiger, at least with its conventional non-nuclear forces, that is. The Putin-Ukraine war is still unfolding but Russia will come out of it severely stunted win or lose and possibly with new leadership. Whatever the outcome, the winner will have a great deal of de-mining to do. The conflict continues to unfold, but regardless of the outcome, Russia is likely to emerge greatly weakened, potentially with a change in leadership.

Putin is a smart guy. Certainly he knows the consequences of releasing as much as a single low yield tactical nuclear weapon, even if it’s limited to a demonstration. Pandora’s box would swing wide open and out would slink an ever-expanding series of repeats of above ground nuclear blasts until a city would be hit. Then all out nuclear war could happen in the old eye-for-an-eye fashion. Dark days would follow indeed.

Putin surely realizes the dangerous situation his county is in with mounting military losses, the brain-drain of skilled workers leaving the country and a crumbling oil and minerals-based economy. Yet he wears the neutral expression of the Sphinx in public because he must. He has painted himself and his nation into a corner. He even resorted to making nice with the plump North Korean dictator which must have been a nauseating demotion for him.

A bit of history

The Magna Carta was an agreement signed in England on June 10th, 1215, at Runnymede along the River Thames. This agreement had the unique provision of the enforcement of limitations on the sovereign. Rather than a simple recitation of grievances by the barons, the Magna Carta contained ‘security clause 61’ which provided for the barons the authority to seize the castles and lands of King John and hold them until such time as he held to his responsibilities as agreed upon in the signed document.

The Magna Carta was not just a contract between wealthy barons and King John, rather it was a step change towards political reform that provided for enforcement on the King. From Wikipedia–

“First drafted by the Archbishop of Canterbury, Cardinal Stephen Langton, to make peace between the unpopular king and a group of rebel barons, it promised the protection of church rights, protection for the barons from illegal imprisonment, access to swift and impartial justice, and limitations on feudal payments to the Crown, to be implemented through a council of 25 barons.”

Unfortunately, the distrust between the barons and the Crown, compounded by the annulment from Pope Innocent III, led to its swift failure. Just a few months after the agreement fell apart, the First Baron’s War erupted. However, this was not the final chapter. The document was reissued in successive versions, with the more radical language removed, in 1217, 1225, and finally in 1297, when its remaining elements were incorporated into England’s statute law. It was not unique in its attempt to limit the power of the Crown; similar efforts were seen elsewhere. Over time, the Parliament of England enacted laws that overshadowed the original document, diminishing its significance.

Back to Russia

The point of highlighting the Magna Carta, despite its failure, is that nothing of this type of significance happened in the history of Russia, at least until the Bolshevik Revolution. Perhaps this comparison is too facile, causing real historians to choke on their Starbuck’s latte. But allow me to finish. The Magna Carta was not entirely unique for its era. However, it was notable for including a provision that enforced the good faith by the King. It represented a collective bargaining effort by the 25 barons with King John to alleviate some of the monarchy’s oppression and, in doing so, progress the political atmosphere for a short time with fits and starts. As kings often do, King John protested to the Pope, who then exerted his authority in a manner only a Pope could. The Pope excommunicated the Barons and nullified the agreement, having been persuaded by King John that it undermined the Church’s authority.

Russia seems not to have a tradition of producing successful popular uprisings to the power of the Tsar. of course, the Bolshevik revolution is the shining counterexample. Not in the sense of overthrow so much, but as an enforceable agreement to relieve a measure of oppression by the monarchy at all levels. In contradiction to this sweeping generalization is the case of Tsars Alexander I and II. Alexander I introduced minor social reforms but he was a strict Russian nationalist and Slavophile. Many of the reforms he instituted early in his career were retracted later.

Tsar Alexander II , however, instituted many liberal reforms but is possibly most revered for his Emancipation of the Serfs in 1861. In the US, he is remembered as the Tsar who sold us Alaska. He was a supporter of the Union in the American Civil War and even sent ships to New York Harbor and San Francisco Bay to deter Confederate warships. Eventually he was assassinated in Saint Petersburg on March 13, 1881. The first assassin’s bomb thrown under his armored carriage left him dazed but uninjured. The second assassin’s bomb thrown shortly thereafter delivered the fatal injuries as he stepped out to investigate. The third assassin’s bomb was unused.

Zooming forward to the present, what actions can the Russian populace take regarding Tsar Putin? After centuries of political oppression aided by new thinking, modern technology, and nuclear weapons the current Tsar has built a deep and wide moat around himself and his allies within the Kremlin establishment. Beyond this moat stands a population conditioned to obedience by fear, a legacy of decades of Soviet rule. I believe that national pride will deter them from emulating Western forms of civil society and governance. And why can’t they develop an authentically Russian something-something ‘democracy’, or whatever? Russia has deep foundation of cultural, artistic and scientific achievements to take pride in, despite its history of authoritarian governance. Whatever Russia eventually does, it will be heavily Slavic and Eastern Orthodox.

Russians are just as pleasant and smart as everyone else in the world, obviously. Russian hospitality is first rate as I have personally experienced. They just have the heavy blanket of oppressive leadership over them that continues to drag through the generations. Even if Putin falls out of power, there is a line of replacements cut from the same cloth. Perhaps a leader of a reform movement could rebuild Russia? It could happen but just as likely it could revert into a system that is better at prosecuting a war of aggression and suppression of the population. The replacement of Putin could be good for the world, or it could go sour. The world has to wait it out and see. In the meantime, it is critical to keep Putin out of Ukraine, Poland and the Baltic states.

The Putin government is like a toxic gas- it will expand into all of the space available. After the decades-long stand down in tension since the collapse of the Soviet Union, the problem of an aggressive Russia arises again. The West must remain the sturdy counter example to the authoritarian culture of Putin’s Russia. We in the USA, especially, need to do a better job as the shining city on the hill. Lately the shine is wearing off.

Chemistry Fun with AI

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Yet ANOTHER chemist bowling the wrong direction. Dammit, Jim!
Multi-tasking in the lab with shoe repair.
Chemist riding a goat. I can think of a few reasons not to do this. But, he DOES have his safety glasses on.
Chemist frying a kielbasa (I think?). At least one thing in the lab smells good.

And finally, a non-chemistry image.

Relaxing after locating a rare Colorado Alpine Cabbage on the way up a 14-er.

Reconstruction of the USA

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Writing about theology is outside my comfort zone. As a non-theist, I lean heavily towards a mechanistic, secular explanation of the universe where observation, measurement and theory are the pillars which support our understanding of the universe. Crediting a deity with creating the universe only begs the question: who created the deity? Why would a universe created by a deity be more likely than one that exists independently? Along this line of thinking, Occam’s Razor would suggest that a deity is an unnecessary step in the reduction to the truth. Occam’s Razor isn’t just philosophical tidiness. It reflects a physics that is cut from the cloth of reductionism.

Occam’s Razor is neither a natural law nor a formal scientific method; it serves more as a heuristic guideline. When multiple explanations yield the same conclusion, the simplest one is usually deemed more likely. Supernatural or magical explanations find no refuge in Occam’s Razor. It’s not about resorting to a simple magic trick. Any explanation favored by Occam’s Razor must still withstand subsequent observation, measurement, and theoretical scrutiny—the core of scientific inquiry.

The point of this essay

I am writing to highlight that the United States of America, despite its chaos and noise, errors and blunders, has developed an impressive economic growth engine, formidable military capabilities, expanded civil rights, enhanced public health, and a wide-ranging scientific and technological foundation that surpasses anything previously witnessed in history. Numerous sources support this claim.

A significant portion of the American experiment including its economic system, directly stems from the European Enlightenment of the 17th and 18th centuries. It must be emphasized that there is an emerging movement aiming to regress various facets of our culture to a period before the Enlightenment—a time characterized by extensive church authority and a government in alliance with it.

I will state plainly that I am deeply opposed to the forces currently working to regress our civilization. Since my earliest memories which began at the time of the Kennedy assassination in 1963, there has been a continuous lament over the state of our nation. People have consistently shaken their heads, openly questioning how the USA could continue to progress amidst the prevailing turmoil. This sentiment has persisted over the years. Nevertheless, not only have we persisted, but we’ve also made continuous progress in improving the quality of life.

The nostalgia for the “good old days” of America’s supposed greatness is often lamented by those who find current times challenging. A closer examination of American history reveals a complex tapestry of both distressing events and prosperous periods. In any given year, one can uncover instances of both success and sorrow. It seems that a certain level of disorder is inherent in our pluralistic democratic republic. The population typically follows a statistical distribution, with a majority of average individuals at the center and fewer at the extremes, represented by the virtuous and the villainous. While disorder is a constant, its nature fluctuates with the changing eras.

Considering the unfathomable expanse of the universe, it is difficult to comprehend the significance of distant galaxies, which remained invisible until recently, within the cosmological framework of the Old Testament as depicted in Genesis. The Abrahamic faiths inherently present a cosmological theory complete with an origin narrative and are replete with Bronze and Iron Age prescriptions for social structure, upheld by a deity who is portrayed as both loving and wrathful- curiously human attributes.

Bronze age religious sentiments

The foundations of these religions originate from an era that is far removed and largely outdated in the context of today’s social norms. The holy scriptures were written at a time when life-changing phenomena were commonly attributed to witchcraft, demons, or benevolent gods. Historically, the struggle to understand cause and effect in life meant attributing disease, illness, and death to dark and unseen forces. The advent of microscopes, along with advancements in medication and surgical procedures, has dramatically altered this perspective.

A persistent and detrimental remnant from the Bronze Age Abrahamic religions is the belief that humans have dominion over Earth and its creatures. This belief manifests in various ways today, notably hindering necessary conservation, environmental and public health efforts out of concern for humanity and the biosphere. The Earth’s biosphere has been under significant strain for many decades. Unfortunately, this broad dominion has historically held over women, who have suffered tremendously under a patriarchy endorsed by these religious doctrines.

Undoubtedly, religion provides numerous benefits to individuals in various significant aspects. However, it can also serve as a personal and collective obstacle. The issue arises when it becomes a foundation for mystical thinking, offering black and white solutions to the complex spectrum of issues we encounter, rather than acknowledging the continuous shades of grey that characterize our reality.

The coming storm

I posted an article on Theocratic Dominionism back on October 25, 2006. Today Dominionism, Christian Nationalism, Christian Reconstructionism, or the New Apostolic Reformation, NAR, are gaining much ground in politics. It is apparent now that the old Republican party has transmogrified into the MAGA party whose devout members are being led to a Christian Nationalism model. The endgame sought is certainly consistent with the goals of Project 2025. This is in the direction of what has been called “illiberal democracy” as the President of Hungary, Victor Orban, puts it.

The father of Christian reconstructionism is credited to the son of Armenian immigrants Rousas John Rushdoony (1916-2001). He was an orthodox Calvinist minister, philosopher, historian and theologian. Michael J. McVicar, associate professor of Religion at Florida State University wrote of Rushdoony –

“As a theologian Rushdoony saw human beings as primarily religious creatures bound to God, not as rational autonomous thinkers. While this may seem an esoteric theological point, it isn’t. All of Rushdoony’s influence on the Christian Right stems from this single, essential fact. Many critics of Christian Reconstructionism assume that Rushdoony’s unique contribution to the Christian Right was his focus on theocracy. In fact, Rushdoony’s primary innovation was his single-minded effort to popularize a pre-Enlightenment, medieval view of a God-centered world. By de-emphasizing humanity’s ability to reason independently of God, Rushdoony attacked the assumptions most of us uncritically accept.” [Italics mine]

According to McVicar, Rushdoony had no interest in the world of the enlightenment. The orthodox Calvinist Rushdoony saw people as “religious creatures bound to God, not as rational autonomous thinkers”. Rushdoony advocated under the theonomic perspective, meaning a Christian form of government where individuals and society are ruled by divine law, especially under judicial laws in the Old Testament of the Christian bible.

Rushdoony opposed democracy which he claimed opposed the will of God and favored the republic which represented a better form of civic government. He said to Bill Moyers in an interview “… a republic avoided mob rule and the rule of the “51%” of society; in other words “might does not make right” in a republic.”

“The central tenet of Rushdoony’s teaching is that God has tasked Christians with taking dominion over society, beginning in Genesis 1:28, in which God commands humans to take dominion over the earth. While many Christians have applied this verse in the context of stewardship, Rushdoony taught that this creation mandate is really a dominion mandate, commanding humans to bring every sphere of society—as well as nature itself—into subjugation under Christ. In his view, Christ’s sacrificial death nullified the Fall and subsequent curse of Genesis 3 and enabled Christians to perfectly follow God’s law. Reconstructionism is a guidebook for Christians to reconstruct society according to Rushdoony’s understanding of Mosaic law. (Notably, his understanding differs dramatically from historical Jewish interpretations and includes stoning LGBTQ individuals.)” Source: The Christian Century, November 2022.

Distilled down to a sticky residue, Dominionism is the belief that Christians should take moral, spiritual, and ecclesiastical control over society. Romans 13:1-5 says in so many words that God has ordained the state as a delegated authority; it is not autonomous. Secular authority is not sanctioned. It is upon this authority that Dominionism rests.

Implementing an ecclesiastical governing hierarchy to operate various government entities will be complex. Individuals identify as Atheist, Catholic, Jewish, Muslim, Mormon, etc., for numerous reasons, including family history or personal choice. Are these individuals considering that sectarianism might not pose an issue? Have they examined the impact of sectarianism in the Middle East and other regions closely?

Even if the sectarian issue is resolved, consider the extensive scope of the law in all its forms. Discussions about biblical law often seem to focus on the Ten Commandments, the law outlined in Deuteronomy and biblical punishments like stoning. Punishing criminals is one aspect, but what about civil laws? The Bible doesn’t explicitly detail regulations for commerce, transportation, safety, torts and numerous other areas governed by secular laws.

An example of religious authority gone bad

The Spanish Inquisition, officially the “Tribunal of the Holy Office of the Inquisition,” began in 1478 by the Catholic monarchs King Ferdinand II of Aragon and Queen Isabella I of Castile. They sought and obtained independent inquisitorial authority separate from the Vatican and its own inquisition. Lasting from 1478 to 1834, this judicial institution aimed to eliminate heresy. However, it often forced Jews and Muslims to convert to Christianity or expelled them from the kingdom when they resisted conversion.

Unfortunately for the people of the New World, the Spanish conquistadores carried their Inquisitional evangelism with them to root out heresy. Along with it they spread smallpox, influenza and other diseases wiping out whole populations. This has been extensively covered by historians. The conquests of Cortes and his second cousin Pizzaro starting around 1519 in what is now Mexico and to the south visited death upon the Aztecs, Incas and many others.

The Catholic church in medieval times carried great authority and the monarchies of the time knew it. They sought to find favor with the Vatican and share in its power and wealth over the population. It manifested as the notion that to be against the ruling class was to be against God. It has never been documented that God had stepped in personally to referee these power games, you know, like he spoke to Noah or Moses, but the church was only too happy step in and be the arbiter of matters for the silent supernatural.

In theocracy, who is in charge?

The Biblical Law scenario wouldn’t involve a deity directly governing society, but rather sectarian politicians and religious leaders would act in the place of the mysterious, invisible and silent Deity. Over time, laws such as those from the Mosaic tradition would need to be codified for widespread dissemination, uniform interpretation and adaptation to law school curriculum. Considering the limited details provided by religious texts on prohibitions and punishments, extensive interpretation would be necessary to address the countless scenarios that could emerge within a society. The question then arises: In cases of uncertainty, what should be the recourse?

The long and short of it

What this burgeoning theocratic movement is about is political power. In short, a subset of the American people believe they have a solution to the woes of society and they have supernatural backing to make it happen. They claim that their authority is not of this world and not subject to Earthly constraints. The laws of man are inherently subservient primarily to the laws of God as issued thousands of years ago to tribal desert goat herders.

Reconstructionism is a quiet movement. It’s purpose is to implement a reconstruction of American values to suit the world view of a minority of religious extremists. It is a movement that seeks nothing less than the establishment of a theocratic form of government in America.  It is also called Theocratic Dominionism or Christian Reconstructionism.  But don’t believe me, see for yourself.  Google these terms and browse the online resources. 

The John Birch Society

For myself, I have been watching Christian fundamentalism since the early 1970’s.  I recall stopping at a booth at the county fair as a high school student and talking to members of the John Birch Society. I thought at the time that they were Looney Toons, or just an obscure Christian libertarian group.  I guessed that they were mostly harmless.   Well, I was wrong.

Frederick Clarkson at PublicEye.org writes- “Reconstructionist leaders seem to have two consistent characteristics: a background in conservative Presbyterianism, and connections to the John Birch Society (JBS).”

He goes on to say- “In 1973, R. J. Rushdoony compared the structure of the JBS to the “early church.” He wrote in Institutes: “The key to the John Birch Society’s effectiveness has been a plan of operation which has a strong resemblance to the early church; have meetings, local lay leaders, area supervisors or bishops.”

The JBS connection does not stop there. Most leading Reconstructionists have either been JBS members or have close ties to the organization. Reconstructionist literature can be found in JBS-affiliated American Opinion bookstores.

But what is reconstructionism about? Again, Clarkson puts it succinctly-

“Reconstructionism is a theology that arose out of conservative Presbyterianism (Reformed and Orthodox), which proposes that contemporary application of the laws of Old Testament Israel, or “Biblical Law,” is the basis for reconstructing society toward the Kingdom of God on earth. “

Reconstructionism argues that the Bible is to be the governing text for all areas of life such as government, education, law, and the arts, not merely “social” or “moral” issues like pornography, homosexuality, and abortion. Reconstructionists have formulated a “Biblical world view” and “Biblical principles” by which to examine contemporary law. Reconstructionist theologian David Chilton succinctly describes this view: “The Christian goal for the world is the universal development of Biblical theocratic republics, in which every area of life is redeemed and placed under the Lordship of Jesus Christ and the rule of God’s law.”

To establish a theocracy is to suppress independent action and thinking. It is to surrender freedom to self-declared religious followers who claim to have been spoken to by an otherwise silent and invisible deity. It is to yield to the argument to “have faith”.

“Deaths in wars and conflicts killed or allowed to die by human decision of approximately 231 million for the 100 years of the 20th Century.” University of Maryland School of Public Policy.

How many of the 231 million people in the 20th century prayed their hearts out and requested help or strength under horrific circumstances? I’d estimate that most of them made every effort within their power.

Conclusion

I agree. It is easy to dismiss this as a bunch of paranoid lunatics. But if you’re paying attention to things, you might also observe that we have been in the midst of this movement for some time.  The inauguration of Trump, and a MAGA Republican majority in either the house or the senate followed by the implementation of Project 2025 will be the kick-off moment for a Christian nationalist takeover of the USA. This is not the country I want to live in.

Risk and Regulations: An Epistle to the Bohemians, Redux.

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Attached is an updated reprint of an essay I posted 10/28/07. Since then I have shifted into EPA regulatory compliance within the chemical industry. My views have changed a little, it turns out.

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“We live in an age of miracle and wonder” is the refrain from Paul Simon’s album Graceland. All around us and through us are engineered materials devised for their specific physical and chemical properties. Time-released magic bullet drugs that inhibit specific enzymes. Flavors & fragrances, colorants, rheology modifiers, UV absorbers, emollients, preservatives, food irradiation and manufactured food additives are engineered and marketed to satisfy our lizard brain’s willingness to shell out cash-for-fun and stimulate our limbic system’s emotive triggers. 

It is hard to avoid contact with manufactured goods that aren’t affected by chemistry. A century and a half of tinkering with substances at the molecular scale has given us the ability to optimize the composition and performance of products that make our lives easier and safer.  Microprocessors and Lycra, Hastelloy and Lipitor- the chemical industry has evolved to produce the raw materials and finished goods needed for the performance we have come to expect.

Industry has a Spotty Record of Safety

Along with the considerable list of positive contributions, history provides a detailed record of the problems associated with the exuberant but uncritical acceptance of the flood of manufactured goods.  From radium poisoning of watch dial painters to chromium VI to asbestos, there is a long list of accidents, ignorance, negligence and environmental insult. The trail blazing of our chemical industry leaves behind it a chronicle of tragedy as well as benefits.

The result of the checkered past of industry is a growing (some would say “metastasizing”) and intertwined web of state, federal, and international regulatory oversight and requirements. And with it- arguably as a result of it- has come greater institutional risk aversion. 

Risk Aversion

In a general way, risk aversion is a type of survival trait and is likely hardwired into our ape brains. It is hard to blame people for being wary or fearful of risks, especially those they do not understand. Over time risk aversion is useful survival trait. But on the other hand, risk aversion is also a type of inertia. Or, it can be a fulcrum from which policy and imaginary justifications are leveraged.  The fear of risk may be firmly grounded on experience or it might be imagined or a mixture of the two. The hard part of risk management is identifying real hazards and the probability and magnitude of a bad outcome for managing safety day-to-day. Basically, the hard part is the whole part.

Risk = Probability x Severity of a negative outcome.

Corporate officers have a fiduciary responsibility to the stockholders. They’re purpose is to maximize profits without undue risk to the organization. Most respond to the regulatory environment by perhaps heaving a sigh and relenting to the requirements. Regulatory compliance can have costs associated with it like animal testing of chemical products and intermediates, or engineering upgrades and these costs need to be built into annual budgetary calculations.

How Granular Does Safety Have to Be?

Can safety practices be excessive? I would say that if some specific activity is based on imaginary risks, risks identified by the untrained or massively overestimated risks, the cold eyes of an industry consultant may be needed. Who knows, you may have actually underestimated a risk.

Safety has a large psychological component to it. How do you compel people to behave consistently in a way that keeps everyone safe? Not just immediately, but in the twentieth or five hundredth time they perform a task with associated hazards? Complacency is a normal human weakness where a misstep can lead to casualties.

The amount and type of safety measures in chemical processing required greatly depends on the chemical substance. Some company’s batch records give very detailed instructions to maintain constant safety. Others are less so on the assumption that the operations staff know what they are doing. Too much detail can lead to operator impatience and freelancing.

It is possible for organizations to be dominated by confident voices that are quite risk averse but not very knowledgeable about the technology. Leaders will state that “safety-first is our policy”.  A paper storm of SOPs will issue, dragging out the most elementary actions into numerous steps and check boxes. There is great merit to SOPs, but enlightened and proactive interpersonal management of hazardous operations is just as important. Management by walking around works.

Organizations can find themselves spiraling into micromanagement of even the smallest details for fear that the regulatory and liability hammer could fall at any moment. Indeed, if one studies many regulations in detail, it is easy to fall into habit of overreacting. Risk aversion isn’t just a personality issue, it is statutory under numerous regulatory umbrellas.

Being a baby boomer, the chemical safety practices I have been exposed to and have practiced is rather out of date. My education occurred during a time when running chemical reactions on an unventilated bench top was normal. We used Tirrill burners to flame dry our glassware on the sophomore organic lab benchtop and set the hot glass on a Transite square, an asbestos product from Johns Manville. I still would have no problem using Transite. In fact, I have done many things since summer of 1980 that would be frowned upon today. My grad school and post doc time went way into the weeds on using hazardous materials with minimal oversight.

You learn how to safely handle chemicals by safely handling chemicals. In the course of using a chemical, you might conclude that the known hazard of the substance appears to be exaggerated, so over time and repetition you let your safety practices loosen up a bit. Then one day, you cross some unseen line and an energetic event happens. While what you did leading to this outcome might be categorized as carelessness, as they drag you out of the lab by your one remaining arm, your ears ringing, a metallic taste in your mouth, and partially covered by your torn and smoldering lab coat, you recognize that you actually learned something from that experience. You now have a better appreciation for the safe operating range for that chemical. You’ve gotten one quantum unit of expertise. This is one way to gain expertise, albeit a painful one. Perhaps it will be useful once you start your next career. I have had many close calls and each one taught me something. Perversely, not having close calls with chemicals- some would call it luck -actually deprives one of practical and useful experience.

Today I am a senior chemist involved in chemical safety in industry. Until recently, I was involved in finding the thermal safety boundaries of chemical reactions through calorimetry. But with the past experience that I have, I know a bit more about the boundary conditions of handling chemicals than the younger chemists may get to acquire. In order to know how to work with hazardous chemicals you must have worked previously with hazardous chemicals and perhaps seen for yourself what can happen with sloppy technique.

This is nothing reckless like poking alligators with a stick in Florida or free climbing El Capitan. I mean things like seeing what actually happens when you pour concentrated H2SO4 into water fast enough right up to the boiling point taking care not to have a splash. Maybe you can see the heat of dilution boiling the water at the H2SO4/water interface.

The Regulatory Environment

Statutory risk aversion is the domain of the state. The name “Nanny State” is a sarcastic descriptor referring to a perceived excess of regulated requirements and conditions in our lives as well as the set of penalties.  Though perhaps well intended, the Nanny State seeks to zero out risk. Even if a situation arises for which there is no explicit regulation, OSHA has the General Duty Clause where employers are required to provide:

“employment and a place of employment which are free from recognized hazards that are causing or are likely to cause death or serious physical harm to his employees…”

This provision exists to address any gaps in OSHA regulations that may not account for unforeseen circumstances. The plethora of regulations is partly due to the vast array of situations in which industrial employees might be injured or killed. Additionally, lawyers have identified and exploited loopholes in the regulations, which are subsequently closed by regulatory agencies. Ambiguities are often resolved through statutory amendments or the application of established case law.

EPA TSCA has the job of generating and enforcing regulations regarding the manufacture and use of a range of industrial chemicals in a limited sector of manufacturing. The central doctrine is from:

As required under section 6(b)(4) of the Toxic Substances Control Act (TSCA), EPA is issuing a rule that establishes a process for conducting risk evaluations to determine whether a chemical substance presents an unreasonable risk of injury to health or the environment, without consideration of costs or other non-risk factors, including an unreasonable risk to a potentially exposed or susceptible subpopulation, under the conditions of use. [Emphasis mine]

TSCA does not include Food, Drugs, Petroleum, Pesticides and a few other areas.

The key words above are unreasonable risk. With every New Chemical Substance filing sent to the TSCA folks at EPA, an assessment must be made by various subgroups for unreasonable risk by the human health group, the engineering group and the environmental group. Thresholds for “unreasonable” have been quantified in order to exclude subjectivity. EPA has many computer models of exposure thresholds, migration in the soil and toxicity to many creatures including humans.

The regulatory environment can make the production of a new chemical substance more expensive or even unfeasible. Nobody advocates the idea that we should be free to pollute and risk the lives of workers and communities.  But even for the most skillful and well-intended, there are many regulatory landmines to dodge: air, water, and waste permits; local zoning; OSHA; EPA (TSCA); fire codes; insurance inspections; MSDS’s in multiple languages; ITAR; and DEA. All have reporting requirements, statutes, and paper trails to maintain.

Pragmatics

There are two kinds of disaster that can bring down a chemical plant. One is obviously a fire or explosion in the plant made even worse by casualties. The other is an administrative or legal disaster. This could be a tax problem or worse like having been determined to be out of EPA regulatory compliance for a chemical release into the environment or worker exposure over time. EPA fines are levied per day per violation.

In my view, the USA began ossifying many years ago in regulatory paralysis in much the same way the EU or Japan has.  The combination of business risk aversion along with the popular sport of outsourcing our means of production only serves to accelerate the de-industrialization of the USA and the EU. At present there is some effort by the semiconductor manufacturers and others to repatriate manufacturing back to the US out of fear of foreign governments using strategic trade regulation as a competitive cudgel.

What can one reasonably do? Consider even if regulations could be softened, this could take a long time. Until such time as there is a change in regulation, it is best to knuckle under willingly. First on the list is to just be compliant with regulations. Even an excellent argument against an “unjust” regulation enforced by an agency will get you nowhere because regulators are legally required to enforce the regulations and fine violators. If you are facing a regulatory judgement, it is well worth having a lawyer who specializes in that area of the law.

Accepting a harsh judgement on your record can possibly hurt you in the future by having a history of serious earlier infractions. A lawyer can search the case law and possibly find a lesser judgement or better interpretation of the regulations. Avoid at all costs the possibility of being found a repeat violator in some future court action. There could be extenuating circumstances that should be taken into account, but this is the lawyer’s domain and is no place for amateurs.

Fiat Lux

In the chemical industry we have regulatory specialists and EH&S departments who keep on top of the regulations and are responsible for maintaining timely compliance. They help keep the doors open and should be appreciated. That said, executives lurking in the C-Suite should be at least conversant in labor and environmental regulation to the point where they know to get advice before issuing directions relating to this.

Note: Obviously I’m not a damned lawyer and my words should not be construed as actual legal advice. I am simply recollecting learnings from my experiences.

Mars and RTGs

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Prologue: I want to give my bona fides on appreciation of the “US space program.” For as long as I can remember I have been a space enthusiast. I followed projects Mercury, Gemini, Apollo, Skylab, X-15, Space Shuttle, ISS, Voyager’s 1 & 2, Cassini and others in real time. Even though space publicists mention scientific research, they never go into more than the very least they can get away with for fear of MEGO- My Eyes Glaze Over. To its credit NASA posts annual lists of research papers with links disclosing research results from R&D conducted in the orbital environment. Here is such a list. Much of the research might seem arcane but it is important to realize that the practical value is likely to come later as others incorporate it into their subsequent research and product development. This is how R&D works.

A few words about Elon Musk’s plans on moving mankind to Mars. As everyone knows, Musk is actively engaged in developing space craft large enough, numerous enough and powerful enough to take a great many people to Mars. His stated dream for humanity is to transport a large number of people to the red planet to establish a permanent settlement- a sort of Earth 2.0 for humans. There is even fanciful talk of terraforming Mars for more convenient and safer occupation. This is a colossal job, even for a small world like Mars.

All energy produced and consumed on Mars will be electrical via nuclear energy, solar, or maybe wind (??) generation. Combustion as we know it is out due to the absence of combustible materials and abundant oxygen. Solar power generation will be limited by reduced solar energy shining on Mars and by the practical problem of dust accumulation. Thermoelectric generation from a Radioisotope Thermoelectric Generator (RTG) has been the solution used on many Mars landers and deep space probes.

The best radioisotopes for RTG are alpha emitters. Alpha particles are +2 charged helium nuclei which cause a large amount of ionization over a short distance as it crams its way through matter, stopping in a short distance. Because they lose energy over short distances even in air, alphas require very little shielding, unlike beta and especially gamma radiation.

Betas themselves are easily shielded, but as they decelerate in matter, they can generate radiation called braking radiation, or bremsstrahlung x-rays, which are more penetrating. This is how x-rays are generated in an x-ray tube. Electrons impacting a target like copper generates x-rays. The effect is more pronounced in higher atomic number (high Z) elements like copper, but in low Z materials like plexiglass x-ray generation is much reduced. Consequently, beta emitters are commonly shielded with plexiglass.

The main downside to RTG is the low efficiency in converting thermal energy to electrical energy via the Seebeck effect– about 3-5 % currently according to most sources. So, for every 100 watts of thermal energy production, only 3-5 watts of electrical energy are available. This puts pressure on the supply of scarce radioisotopes.

On the good side of RTGs, they are stable, reliable and long lasting. Waste heat can be used to provide warmth for proper operating temperature in the craft or facility. The Mars lander Curiosity uses 4.8 kg of 238PuO2 to produce 100 watts of electrical power.

The deal with the devil you have to make with RTG power generation is that the best heat generating isotopes in terms of power density (watts/g) also have the shortest half-lives. For instance, 210-Po has a high power density of 140 watts/g but a half-life of only 0.38 years. It undergoes a 5.6 MeV alpha decay directly to stable 206-Pb, emitting a gamma only once in 100,000 alpha decays. Gamma emission poses shielding weight penalties and radiation hazards both in manufacture and operation in space. Even with no humans around, there is still the matter of electronic components that are sensitive to radiation. The more commonly used alpha emitter 238-Pu has a lower power density of 0.54 watts/g but a reasonably lengthy half-life of 87.7 years and minimal shielding requirements.

The background radiation environment in space by itself demands that shielding and radiation hardened electronics be used. Any added radiation from an on-board RTG only compounds the problem. The amount of shielding any given material provides is measured in half-thickness, not “full thickness” and is dependent on the type and energy of the particle. This value is the thickness of a specific material required to reduce the intensity to half of the incident radiation, not the total radiation emerging from the shielding material. This is because scattering can occur within the shielding material contributing to or minimizing the total flux. The point of this is that shielding only attenuates radiation to acceptable levels and not to zero.

238-Pu is a synthetic isotope that must be isolated from other Pu isotopes as well as a dog’s lunch of other elements in spent nuclear fuel or be selectively synthesized by nuclear chemistry. Isotopic separation of 238-Pu from other plutonium isotopes is difficult, slow and not the preferred method of producing it at scale. Nuclear chemistry that provides exclusively 238-Pu from a single transformation as with like 237-Np, offers a more productive route. This allows good old regular, valence-electron chemistry to effect the separation needed.

Source: Wikipedia. A pellet of 238PuO2 glowing from decay heat.

238-Pu is produced by neutron irradiation of 237-Np producing transient 238-Np with its 2-day half-life and subsequent beta decay to the 238-Pu. Chemical separation of the plutonium from residual neptunium is straightforward but, like all chemistry with radioisotopes, burdened by the need for radiation shielding for safety.

238-Pu is presently in short supply in the US. The Savannah River Site was producing “bulk” 238-Pu but was shut down in 1988. After closing of Savannah, the US purchased 238-Pu from Russia but the word is that Russia is short on it as well. In recent years other sites have been scaling up production where “scaling up” means producing in the several hundred grams to a few kilograms in a campaign.

Source: Wikipedia. Just an example of an existing RTG generator.

In the RTG, plutonium is not used in the metallic state but as the oxide which is a ceramic or refractory** material like most heavy metal oxides. The plutonium is oxidized to 238PuO2, pelletized and clad in corrosion resistant iridium. According to NASA, this refractory form of plutonium is resistant to an accidental release in a variety of accident scenarios including Earth reentry and rocket propellant fires.

Source: NASA. 238-Pu clad in iridium for use in RTGs.

The Seebeck effect is not the only means of producing electrical energy from radioactive decay heat. The free piston Stirling Radioisotope Generator can use decay heat to drive a piston in a Stirling engine using helium gas as the working fluid. Waste heat is dumped at the cooled end of the engine and the linear reciprocating motion of the free piston is used to generate electrical power in the adjacent alternator.

Electromagnetic flashlight.

The electric alternator is similar to the electromagnetic flashlight on the market. It works on the ordinary induction principle buy moving a magnet through a coil. You shake the flashlight to recharge it, causing the internal magnet to move back and forth through a coil. Shake it for 1 minute to get 4 minutes of light. The Stirling radioisotope free piston linear alternator operating in this manner can produce 4 times the electrical power of an RGT.

Source: Free-Piston Stirling Engine Technologies and Models: A Review, Carmela Perozziello; Lavinia Grosu; Bianca Maria Vaglieco, Energies 2021, 14(21), 7009; https://doi.org/10.3390/en14217009

In 2020 workers Wong and Wilson at the NASA Glenn Research Center reported that they were able to operate a Stirling radioisotope power convertor for 14 years maintenance-free. 

Off we go!

Some thought will be needed on screening potential migrants to Mars for age, various physical ailments, dental health, genetic predispositions, sociability and underlying psychological issues. A manic crew member could drive fellow crew members to a murderous rage over time. Such screening has been done with astronauts for a long time. I wonder if choosing to migrate to Mars isn’t a sign of some precarious psychological condition in itself, after all the likelihood of a return to Earth may be slim. It would resemble going to jail in some ways.

Over time, the masses of new Martians living in Muskville will have to decide on what to do with themselves beyond exploratory geology, meteorology and engineering studies of Martian accommodations. Mars is a big, arid and frigid desert with no breathable air. But it may offer a few choices for recreation such as spacesuit hiking and shuffleboard. The outdoor choices will be limited by the Muskvillager’s battery, heating and oxygen supplies as well as ability to get around.

Eventually, all manner of psychological, social and physical maladies will manifest in Muskville and will have to be dealt with. People will spontaneously form cliques eventually giving us-vs-them issues requiring mediation. Unless the New Martian settlers are sterilized, pregnancy is a near certainty. An entire book could be written on complications this would bring. The alternative is to limit the inhabitants to a single gender or to gay individuals- most likely a non-starter.

Death on Mars means that your remains will need to rest somewhere outside the facility. A fresh body will freeze stiff in the Martian cold and remain that way indefinitely. Digging a grave will require energy expenditure and digging tools. Cremation will consume considerable power and may be out of reach.

Something like a hospital with medical supplies and trained staff will have to be present. The few physicians who might be present will be required to be generalists with exceptional diagnostic and surgical skills. A full medicine cabinet to cover a range of maladies will be needed to support this.

As Muskvillagers age out, the range of health problems will widen and require care. Diabetes, cancer, dementia etc. will fade in and people will age and die. This will leave job openings and duties behind which will have to be filled.

In general, the conveniences of modern living will be seriously cut short for the New Martians for a long time. A supply line with Earth that can withstand politics, business failure and war must be maintained.

If I were planning a migration to Mars, I’d worry about maintenance and spare parts for everything. Mechanical things will break. Perhaps an orange-colored Home Depot module will hitched to the back of the lander and sent along with a load of duct tape, assorted bolts and screws, sealant, O-rings, hand tools and cleaning supplies. Don’t forget a few bags of peanut M&Ms.

Wherein I jump to conclusions.

The human capacity for folly knows no bound. Woven in with folly are variable education, emotional inputs and diverse belief systems. The migrants will carry religious and political predispositions that they may or may not reveal in screening for candidates. Friends and relatives on Earth will sicken, age and eventually die but access to a return trip to earth may be severely restricted or effectively impossible.

On reflection, establishing even a modest Mars base will involve large energy inputs. Getting to the surface of Mars with enough reserve propellant for the return trip, the establishment of shelter, oxygen and water supplies are the priorities. Beyond just surviving day-to-day, there is interest in the possibility of putting Martian minerals to use as building materials or even water and oxygen production.

There are indications of frozen water on the surface of Mars in certain limited locations. Where there is water there is the possibility of using electric power to produce oxygen. The hydrogen produced may have utility somewhere but its use for combustion seems unlikely due to the corresponding amount of oxygen needed.

Anywhere you have silicates, aluminates and metal oxides, you have oxygen. Silicon and aluminum both have a strong affinity for oxygen and as such represent a thermodynamic well requiring steep energy inputs for oxygen extraction from minerals. Even worse, many silicates and aluminates are oligomers, chain polymers or network polymers that render them insoluble solids with high melting points. Silicates, aluminates and metal oxides are all comprised of a central atom- silicon, aluminum, or a metal -that are electron deficient by virtue of being connected to oxygen anions. In order to liberate oxide from oxidized silicon, aluminum or a metal, something negatively charged needs to come in and displace the oxide species. Metal oxides like the iron oxides are very often refractory requiring high temperatures to react. Then there is a long list of oxyanions like sulfate, phosphate, hydroxide, chromate, ferrates, molybdates, titanates, tungstates, manganates, etc., each with metal cations. After these there are the polyoxyanions …

The point is that there are a wide variety of oxide species to be found in rock and soil with differing properties. In the end, a negatively charged oxide anion must be oxidized to produce molecular oxygen.

A thermodynamic well resides in a substance where atoms come together to form strong chemical bonds and release a great deal of heat into the surroundings. The same amount of energy that was released is minimally what would be needed to drive the reaction in the reverse direction. This bond forming heat energy is dispersed amongst the large number of surrounding molecules. The heat evolved in forming the original bond produces a high temperature locally, but as it spreads out each succeeding layer of neighboring molecules gets a smaller and smaller share of the original energy. As the bond forming energy release is spread over more and more molecules, the resulting temperature rise of the succeeding layers get smaller and smaller.

Newton’s Law of Cooling says that rate of heat flow is directly proportional to the temperature difference between contacting objects. The greater the temperature difference, the more useful work (heat and work are both energy) that can be done. Large temperature differences transfer large quantities of energy. Low temperature differences result in less energy transferred. As the heat spreads to the surroundings it produces decreasing temperatures as the heat conducts away and the ability to do work diminishes. This constrains the recovery of waste heat.

The diffusion of energy in this manner is what entropy is about- the irreversible loss of energy to the surroundings. If you are tempted to talk about entropy, consider that it has to be consistent with its unit of measure: Entropy, S, equals energy per degree Kelvin or Joules/Kelvin (J/K).

In order to get molecular oxygen from minerals it will require a great deal of energy expenditure per kilogram of oxygen. Not only that but specialized equipment and chemicals. Any oxygen produced will have to purified and compressed into cylinders.

MOXIE

The extraction of molecular oxygen from the abundant carbon dioxide atmosphere seems desirable and has actually been put to the test on Mars. A prototype molecular oxygen generator called MOXIE went to Mars on the Perseverance rover and successfully produced oxygen from carbon dioxide beginning in 2021.

Source: NASA. The MOXIE package installed on the Perseverance rover.

The MOXIE oxygen generator is a solid oxide electrolysis device that operates at 800 oC and uses a stack of scandia stabilized zirconia ceramic electrolyte. An excellent source of information on MOXIE can be found at this Science site.

About 10 % yttria (Y2O3) or scandia (Sc2O3) will prevent the zirconia (Zr2O4) electrolyte from undergoing a phase change that causes the ceramic to fail at high temperature. From personal experience I know that scandia is chosen as a better diluent for zirconia because it allows lower temperature operation than yttria by perhaps 200 oC. The lower operating temperature with scandia allows for better sealing of the cell. High temperature seals are very problematic at these operating temperatures.

The MOXIE electrolysis cell uses a nickel coated cathode for reduction of the CO2, a ceramic zirconia/scandia electrolyte that allows oxygen anions to selectively pass through, and an anode where the anions are oxidized and combine to form O2 where it is captured. MOXIE produced O2 at a rate of 6-8 g/hr while on Mars. The process vents carbon monoxide waste as well as unreacted CO2 at the cathode where it is vented.

A limiting factor in operating MOXIE is the operating voltage across the cathode and anode. Two kinds of chemistry can occur within MOXIE. Carbon dioxide can be reduced to form oxide or carbon, depending on the flow rate of CO2 and the operating voltage. The Nernst voltage, VN, is the minimum voltage necessary to do the chemistry. At about 1.1 volts the cell will reduce CO waste biproduct to carbon on the cathode. This is called “coking”. Carbon formation on the cathode impedes the function of the cathode and reduces the output of the cell. The voltage for coking varies very little with flow rate.

The VN for the desired reduction of CO2 to oxide (O–) and CO at a low flow rate is around 1.0 volts and at high flow rates drops to about 0.95 volts or just a bit lower. So, the “normal” operating voltage range then would be between 1.0 and 1.1 volts to prevent fouling the cathode with coke. The operating voltage window seems a bit narrow. It was found that while a stable operating voltage could be supplied, the resistance of the cell was very sensitive to temperature making stable operation a bit delicate.

Pyrochemistry

Extraction of oxygen from lunar mineral samples has been done previously (below). All of the mineral samples were iron rich and gave yields of 2 to 5 % in the form of water. The samples were from Apollo 17 and consisted of ilmenite (FeTiO3), basalt, soil and volcanic glass. The process uses hydrogen at a reaction temperature of 1050 oC producing H2O. Presumably the water vapor is mixed with hydrogen during and after the reaction. The water can be isolated by simple condensation in the presence of the hydrogen.

Reduction of Ilmenite:  FeTiO3 + H2 — > Fe + TiO2 + H2O

Source: Oxygen Extraction from Lunar Samples
by Carlton C. Allen
Lockheed Martin Engineering and Sciences Co.

To use the process described above, high temperature is required for the hydrogen reduction in a refractory vessel. This requires considerable electrical energy input to heat the thermal mass of the vessel and the regolith. Spent material will have to be removed and discarded. Perhaps the heat can be recovered for general facility heating. Oh yes, the recovered water will need to be electrolyzed to produce molecular oxygen and hydrogen. This process will use plenty of electric power as well as for the compressors to store the O2 in pressure bottles. In principle the hydrogen can be recovered for reuse in the hydrogenation vessel.

The above process applied to ilmenite produces metallic iron and titanium dioxide, a white pigment. FYI, ilmenite is a common raw material for high purity titanium dioxide production. It is high purity because the titanium dioxide is prepared from titanium tetrachloride which is isolated by distillation from the ore matrix after fluidized bed chlorination.

The first Martian settlers will have to bring every single thing necessary to live on the planet. That includes launching it and landing it on the surface intact. Landing on Mars is tricky because the atmosphere is too thin to provide much aerobraking. The Martian surface pressure is the same as the Earth’s at 80,000 ft altitude and the temperatures are frigid.

Let’s say we successfully land a crew and set up housekeeping. What are they going to do with their time? These missions are supposed to last about 2 years including a lengthy transit time. They can collect various kinds of data on Martian geology and weather and send it back to earth. Somebody will get publications out of it. Eventually, somebody will decide that there must be other things to do besides geology and meteorology. Naturally there will be much ongoing R&D on the pragmatics of living on a remote Martian outpost in a crowded pressure can.

Eventually, the question of what non-research living will look like. Shelter will need construction from some kind of materials. Every new section of shelter will need to be airtight and equipped with environmental controls, sanitation and power. Bulkheads between sections will need to be in place to isolate calamities.

Support staff will be needed one day to provide critical services and perform facilities maintenance. This would also include medical staff, emergency care, food & sanitary support, electronics and IT support and administrative staff for the inevitable paperwork. The lander will need rocket engineers for upkeep and repairs to assure launch reliability for the return trip. Do rockets exist that can sit for a year fueled and then reliably launch and insert into a trajectory back to Earth? There are many, many problems to be resolved in many areas.

After some period of time, a crime will happen on Mars. It could be petty theft, assault or even murder. Someone will have to be appointed to look after law and order. An astronaut-sheriff, sergeant at arms or just the po-leese. What kind of due process will be available to a suspect in a Martian colony? Guns will be too risky to have in the settlement given that a bullet could pass right through a bad guy and rip through the structure creating a leak.

On earth, doing independent research requires getting academic credentials, finding a position, grading exams for goddammed freshman chemistry, executing an R&D program, and then going home every day to refresh and have a social life. Imbedded in all of this we have courtships, marriage, mortgages, babies and divorce. We manage the ten thousand details of modern life and interact with our families and social networks. We mourn those we lose and celebrate our achievements. We enjoy good health and suffer injury and sickness and eventual death.

On Mars, the equation will be a bit different. Many of the above life elements will apply, but from a great distance. Instead, we will be confined to a small space with an unchanging group of fellow crew members. The distance to Earth from Mars is constantly changing and there will be a period absent any communication when the earth is behind the sun.

Eventually, research on living in space or on Mars will wind down to minutae if it hasn’t already and people will have to find other things to do. The funding for living off-world will have to switch from R&D to … what, a lifestyle? 

I wonder if there will ever be room for commerce and jobs on Mars. I can see running a canteen or restaurant for profit but stocking them with earth supplies will be prohibitively expensive and infrequent.

What joy can there be living in a pressure can on a hostile planet? What few hermit-astronauts there may be might find it acceptable if they never need a dentist. Perhaps dentures or implants should be routinely fitted to all visitors to Mars.

The second stage of Mars exploration will have to ramp up progress on sustainability. Using Martian soil as raw materials for construction and for crops. As the Martian population rises beyond the first few rotating crews, what will the immigrants do with their time in can-living on a hostile world? Would going to Mars to lead an utterly confined life with nothing to do be an attractive draw?

Epilog

I think that settling on Mars is not such a great idea overall and specifically would be wasteful of resources that should be applied to the rehabilitation of the biosphere on our home world. It would somewhat resemble living on the Amundson-Scott Station on the south pole but without the benefits of breathable air or supplies regularly shipped in. Further, the lack of radiation shielding on the surface of Mars will offer 40-50 times the background radiation as on Earth, not counting the occasional storm of angry solar protons the sun flings out now and then.

** NASA does not use the terms “ceramic or refractory” in its description of the 238-Pu heat source. This is my choice of words.