H. Holden Thorpe: "This may be the most shameful moment in the history of U.S. science policy."

This week's editorial in the journal Science, written by the Editor in Chief of this prestigious scientific journal, comments on Trump's decision to lie to the American people about Covid-19, thus killing and severely injuring large numbers of them:

EDITORIAL: Trump lied about science (H. Holden Thorp Editor-in-Chief, Science Journals. Science 18 Sep 2020: Vol. 369, Issue 6510, pp. 1409)

My fellow married old farts: Do you love to look at pictures of your spouse when he/she was young?

My wife was 22 when I married her, just turning 21 when we moved in together.

I love her very much decades later, in ways that matter far more than when it a big part of my love for her was involved with the fact that she was incredibly sexy, but I still find myself looking at her when she was young, when that odd thing was so important.

I don't know what I'm trying to see in those pictures. What am I trying to see, what is the yearning? In a way, it almost feels perverse.

Of course, no real disrespect, but now 21 year old people seem so much like kids - smart kids to be sure, kids perhaps wiser than I was at 21, better kids than I was at 21 to be sure, fine kids - but they're still just kids.

It is strange, though, because it occurs to me that as I have always seen my wife as a full woman, when I was just living with her, when we first married, but was she just a kid? Am I really looking at a full grown woman when I look at those pictures? Was there something of "just a girl" there?

There are many things that are wonderful about growing old, powerful perceptions, but many things that seem more mysterious than ever and in some sense disturbing: The challenge of the veracity of memory is one of them.

I took a day off from work, and spent it with her, walking around downtown Princeton, masks off for lunch on a sidewalk, and suddenly I'm struck by a kind of wonder...how I wonder...how did the time go away?

Noninvasive Assessment of Traumatic Brain Injury by LC/MS/MS Determination of 8 Urinary Metabolites.

The paper I'll discuss in this post is this one: Simultaneous Determination of Eight Urinary Metabolites by HPLC-MS/MS for Noninvasive Assessment of Traumatic Brain Injury (Shi et al., J. Am. Soc. Mass Spectrom. 2020, 31, 9, 1910–1917).

When your Doctor orders blood or urine tests to obtain information about your state of health, the general term for the analyte being measured is a "biomarker." Blood levels of glucose, or A1C, for example are biomarkers for diabetes, cholesterol, a biomarker for heart health. Quietly, without much fanfare, there has been a revolution going on in the determination of biomarkers with increasing sensitivity. To some extent, this revolution - at least originally - was involved in something known as "competitive binding assays" or "ligand binding assays." When I was a kid I used to make reagents for these assays that were labeled with radioactivity, "RIA" reagents, "radioimmunoassay" reagents; almost no one uses this technology anymore, it has been supplanted by ELISA, enzyme-linked immunosorbent assays, in which the radiation detected is of much lower energy than is provided by radioactive materials: It is the radiation we know as "visible light." I expect that within a decade, much of the ELISA testing will go the way of RIA, supplanted by mass spectrometry, or at least in tandem with mass spectrometry.

Mass spectrometry, in general, falls into two classes, "triple quads" which provide high sensitivity for the "work a day" world - including commercial medical laboratories, and in research, high resolution (where resolution refers tp mass accuracy) mass spectrometry, which can be of several types, "orbitrap," "time of flight" as well as the much rarer but incredibly accurate "Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICRMS).

A recent trend has been to approach combining high resolution mass specs with high sensitivity; this trend is only going to continue.

In the absence of validated biomarker analysis, diagnosis can involve considerable risk. Personally, I have an unusual EKG. Since I was a young man, doctors have often interpreted my EKG as implying that I have had - or am having - a heart attack. I've actually been hospitalized several times because of this, and once was briefly admitted to ICU, despite the fact that I have not had a heart attack. The second time I went through this process, my physician recommended that I have an angiogram, which involves inserting a catheter directly into the heart. While the test is very cool - you're on a local anesthetic and can actually watch the chambers of your beating heart on a television screen along with the doctor - it also is fairly risky. I had to sign all sorts of releases stating that I was aware that the test could either severely injury me or kill me. (There is a non-invasive biomarker test, "cardiac enzymes," troponins, that can indicate an active heart attack - but the damage done by previous heart attacks - I've had this test a number of times.

The situation with respect to the brain is even more complicated. Although in recent years many technologies have been developed for brain imagining, since the brain is an organ where many problems, for example Alzheimer's, actually take place on the cellular or molecular level.

The instrument utilized in this paper is certainly not a "state of the art" instrument, but it is a solid instrument that was widely in use ten or fifteen years ago, and was very popular, bordering on something of a scientific "cult" - the Sciex API 4000, a triple quad instrument. This lab, at the University of Missouri is probably not funded enough to drop half a million dollars regularly on the latest and greatest mass spectrometer every two or three years. Nevertheless, it's good work, which can lead people - some of whom will have more advanced instrumentation - to have something on which to build.

From the introduction:

I spent 3 1/2 hours last night listening to Amon Goeth's (Schindler's List) former slave talk...

...about her life as his slave.

(I have recently renewed study of this period because of am better understanding, because of our Nazi "President" how it happened.)

It was an interview as part of USC's Shoah project, which features living history videos. The video is the testimony of Helena Jonas Rosenzweig, one of "Schlinder's Jews," who actually lived in Goeth's house.

She was an articulate speaker with such overwhelming depth of humanity; she died in 2018, and interviewed when she was 71.

In the movie, Schinder's List, she was represented by a composite character, as she was one of two housekeeping slaves held by the vicious camp commandment, the war criminal Amon Goethe, who was executed by the Poles in 1946.

Zero to the start: The interview begins a few seconds after the test pattern.

Revealing Mechanistic Processes in Gas-Diffusion Electrodes During CO2 Reduction to CO/Formate.

The paper I'll discuss in this post is this one: Revealing Mechanistic Processes in Gas-Diffusion Electrodes During CO2 Reduction via Impedance Spectroscopy (Bienen et al., ACS Sustainable Chem. Eng. 2020, 8, 36, 13759–13768)

Electricity is decidedly not a primary source of energy, and as such, it is always a thermodynamically degraded form of energy. It is therefore intrinsically wasteful. Storing electricity - generally as chemical energy although there are limited opportunities to store it as gravitational energy or as compressed gases - further thermodynamically degrades electrical energy and also is intrinsically wasteful both at the point of storage and at the point of release. Batteries, for example, give off heat, charging and discharging. Despite vast enthusiasm for energy storage by the general public, and tens upon hundreds of thousands of papers written on this subject, all of this is generally true, as I often state in my posts in this space.

There is one caveat however that is possibly of some possible import - if one captures energy that would have been wasted anyway and stores it in a form that is usable - the thermodynamic losses, although there still will be losses, will be minimized. At the most extreme, the only form of primary energy is nuclear. The sun is famously a nuclear device, which drives the wind, provides light - which over hundreds of millions of years was converted into chemical energy, dangerous fossil fuels which we can't burn fast enough - and also into current inventories of biomass, including but not limited to food. Some of the very best minds of the 20th century learned how to harness nuclear energy in the form of fission, although strictly put, uranium and thorium and the elements made from them are actually stored energy from ancient supernovae. Indeed, geothermal energy, which is provided by heat released by nuclear decay is also stored energy from ancient supernovae, being released in a generally regular way, earthquakes and volcanoes not withstanding. Only tidal energy is seemingly divorced from the nuclear primacy.

Nevertheless in practical engineering terms, we tend to think of dangerous fossil fuels and related biomass as primary energy, light from the sun as primary energy, wind as primary energy, geothermal as primary energy, gravitational energy, which is used in tidal and hydroelectric systems (the latter still driven by the sun) as primary energy, and of course, nuclear fission as primary energy.

The paper listed at the outset of this post is about wasting energy to make electricity and then wasting even more of it to make chemical energy, in this case formate and carbon monoxide, the latter, via the "water gas" reaction, an equivalent of hydrogen.

Despite my contempt for the thermodynamics of electricity, I do sometimes imagine cases where it might be acceptable to waste some energy to make electricity, and even chemical energy via electricity.

To illustrate, I offer a diversion. Over the last week or so, at various times of the day, on various days of the week, I've been downloading the data and graphics on the CAISO systems status pages, in three areas, demand, supply, and emissions. CAISO monitors and oversees electricity in California, CAISO = CAlifornia Independent System Operators. They have these wonderful real time page with graphics and numbers that will tell you the state of affairs with respect to electricity at any moment of the day. It's here: CAISO Pages

Here are some graphics I downloaded a little while ago as of this writing, near the 17th hour of the day, Pacific Time:

Here is the demand for electricity in California; the shaded area is historical data for the day, the line beyond is the predicted electricity demand.



The 17th hour, 5 pm PST or PDT +/- an hour or two, as the case might be is consistently close to the peak demand for energy in California, weekends, work days, holidays, every day.

Most people know that the sun is "going down" around that time, and as a result the output of solar energy is declining. California is unique among those places invested in the "renewables will save us" fantasy, in that the output of solar energy can dominate, at times, the output of so called "renewable energy", at least around noon.

This graphic and data breaks down what percentage was around the 17th hour of September 15, 2020:



This graphic and data shows the data for the September 15, 2020 up to 17:10 (5:10 pm):



The absolutely flat grey line near the bottom, 2,241 MW, is California's last remaining nuclear reactor, Diablo Canyon, two nuclear reactors contained in a single building. From midnight until 7 am this morning, it was producing just about as much energy as all of the wind turbines, solar cells, biomass combustion plants (which almost certainly include garbage incinerators), and geothermal plants in the entire state.

The disturbing line, of course, is the "imports" line and the "natural gas" line.

Here are California's emissions, as of 17:10 (5:10 pm PDT).



Don't hold me to this, but my general impression is that if you were to average all the "per hour" emissions data I've seen over the course of pulling up and downloading 20 or 30 of these files, the average would be somewhere between 7,000 metric tons and 8,000 metric tons of carbon dioxide ruthlessly dumped by the State of California to provide electricity to its citizens.

There are 8,767.76 hours in a sideral year, suggesting that California dumps about 65,750,000 metric tons of carbon dioxide into the planetary atmosphere each year, this while being "green" and regularly passing, going back to the wonderful time I lived in that State, now decades ago, "by 2000" and "by 2020" and "by 2050" and "by 2060" energy bills claiming that the state will be "green," at least as they imagine "green."

To be honest, my contempt aside, this actually isn't bad, and on their emissions page they have one of those innumerate "percent talk" statements about how great they're doing on emissions.

The reality is however, that all this talk, half a century of it, has not addressed climate change. California, and Oregon, and Washington, recently Australia, this week the Pantanal, are all burning, and powerful hurricanes slice through the Southeastern and Northeastern United States like coupled freight trains.

We needed to be releasing zero carbon dioxide into the atmosphere to generate electricity, and we needed to be doing it years ago.

I just went on the CAISO site again: Today's peak electricity demand took place at 17:18 this afternoon, at 35,971 MWe.

Diablo Canyon is not very impressive in terms of its thermodynamic efficiency with respect to its "primary" energy. Like most nuclear power plants designed in its era, it's around 33% efficient, atrocious really, but similar to all historic Rankine cycle plants. Modern gas powered plants, which are combined Brayton/Rankine cycle plants are closer, and sometimes exceed 50% efficiency.

The reality is, that today, to have provided all the electricity for today's peak demand, 35,971/2,241 would require 17 buildings the size of Diablo Canyon of Diablo Canyon's precise design - which is, by the way, going to be shut in three or four years, because it's "too dangerous" in the minds of people who can't think very well, but the huge tracts of the state burning each year is not "too dangerous."

Of course, at around 3:40 am on September 15, 2020, the demand for electricity in California was less than 22,000 MWe, and the bulk of the putative imaginary nuclear power plants would not be necessary.

In general, my thermodynamic sense is that it is stupid to generate electricity to create potential chemical energy. It is much smarter to use direct thermal to chemical energy conversion if one were to store energy.

However, all chemical processes require cooling, and the rules of process intensification, which are rules to derive the most usable energy per unit of primary energy generated, can conveniently convert thermal energy to electricity with Rankin or Brayton or Stirling heat engines, and storing this mechanical energy may be justifiably be done with an electricity intermediate.

The chemical process in the paper that I promised to discuss at the outset uses carbon dioxide as a feedstock; if this carbon dioxide is obtained from the waste dump into which we've transformed our planetary atmosphere, that can help clean it up.

Here is the cartoon associated with the paper's abstract, which can be read at the link:



From the introduction to the paper:

All countries that signed the Paris agreement have committed to reduce greenhouse gas emissions according to the target to keep global warming well below 2 °C with regard to preindustrial values. This entails significant efforts to reduce the carbon footprint of all sectors in the following decades. Because industrial processes significantly contribute to the overall emissions of industrialized countries, for example, in the EU-28 with 8%, the development of innovative routes with lower or negligible CO2 emissions that can substitute traditional processes based on fossil resources can make a contribution to achieve the desired targets.(1?3) The electrochemical conversion of CO2 using renewable energy not only substitutes conventional CO2-intensive processes based on fossil resources but also utilizes CO2 itself as a feedstock, thereby making it a valuable carbon source.(4?6) Depending on the catalysts and reaction conditions, several carbon-based products can be obtained by the cathodic electrochemical reduction of CO2.(7,8)

This work focuses on the tin-catalyzed conversion of CO2 to obtain formate as the target product. Typically, CO2 is not solely converted to formate (eq 1) on tin catalysts but also to carbon monoxide to a lower extent (eq 2), while the aqueous electrolyte is reduced to hydrogen (eq 3) in a parasitic side reaction, reducing the charge efficiency with respect to formate formation, according to the following equations (1) (2) (3)



Formate can be used as a deicing agent or drilling fluid as well as for tanning and silage when protonated to formic acid.(9) In a proof-of-concept study, it was also shown that formate obtained via CO2 reduction reaction (CO2RR) can be utilized as energy carrier and fed into a direct formate fuel cell to produce electricity or after catalytic decomposition to hydrogen with subsequent re-electrification in a typical polymer electrolyte membrane fuel cell.(10,11)

Unfortunately, the conversion of dissolved CO2 on planar electrodes is limited to a maximum current density of well below 10 mA cm–2 because of mass transport constraints evoked by the low solubility of CO2 in the aqueous electrolyte (33 mM L–1 in H2O, 25 °C, 1 atm) and the diffusion of dissolved CO2 from the bulk electrolyte to the electrode surface.(7,12,13) This limitation can be circumvented by the use of so-called gas-diffusion electrodes (GDEs) providing a porous architecture and intensifying the contact between the gas-, liquid-, and solid phases. Their use entails a substantial increase in the number of active sites while the diffusion length of dissolved CO2 to the catalyst surface is reduced. Accordingly, gaseous CO2 can be employed as the substrate and, due to the above effects; the macroscopic mass transport of the reactant is substantially accelerated.(14?16) As a result, the achievable current densities when using GDEs for CO2 electrolysis can be increased by more than an order of magnitude compared to planar electrodes without sacrificing selectivity toward CO2RR products.(17?19) The so far achieved current densities which are already on industrially relevant orders are the reason why GDEs have gained increasing interest in recent years for the investigation of CO2 electrolysis systems.(15,19?21) Nevertheless, long-term stability of these GDEs is an under-represented research topic in the literature. Besides potential catalyst degradation, GDEs might suffer from a change of their hydrophobic properties over time, resulting in flooding, efficiency losses, and in a shift of the product selectivity toward the undesired hydrogen evolution.(22,23) In that respect, electrochemical impedance spectroscopy (EIS) is a powerful tool to deconvolute contributions of specific physical and (electro)chemical processes to the overall resistance during operation of electrochemical devices. The knowledge which process (e.g., charge-transfer, mass transport of reactants) determines the polarization resistance gives valuable insights required for the rational optimization of the employed GDEs and can aid in revealing possible degradation mechanisms. To use EIS as an electrochemical diagnostic tool, it is crucial to know which physical phenomena are observed in the measured impedance spectra...

He bought her a diamond for her throat; he put her in a ranch house on a hill...

I wish I had a river so long...

Power ideals and beauty fading in everyone's hand...

Hidden Perils of Lead in the Lab: Containing...Decontaminating Lead in Perovskite Research.

The paper I'll discuss in this post is this one: Hidden Perils of Lead in the Lab: Guidelines for Containing, Monitoring, and Decontaminating Lead in the Context of Perovskite Research (Michael Salvador,* Christopher E. Motter, and Iain McCulloch, Chem. Mater. 2020, 32, 17, 7141–7149)

When I was a kid, I worked a few years with radioactive iodine-125 to make reagents for an early and once popular form of competitive ligand binding assays; radioimmunoassay kits. The radioactive iodine came in the form of an iodide salt, and the procedure was to oxidize the iodine with a reagent called "Chloramine T," N-chlorotoluene sulfonamide, an oxidant that generates the electrophilic reagent chloroiodine and, inevitably, some free iodine, which can and does volatilize. The chloroiodine would react with aromatic rings - most typically on tyrosine in proteins, and the protein (or other standard) would be thus labeled and detectable at very low levels using a scintillating detector, but some would always escape from the test tubes in which the reactions were performed.

Although iodinations were conducted in the hood it was inevitable, especially because chromatography was generally conducted on benchtops in this lab, that surfaces in the lab would become contaminated with radioiodine, including floors and benchtops, and ultimately the result that scientists working in the lab would themselves become contaminated. Most everyone had a thyroid count after a few months, but one could minimize it by taking iodine supplements, something I encouraged among my peers.

The fun thing was that one could almost always see where and how much one was contaminated with the simple use of Geiger counter, and one could discover quite readily how effectively one's safety practices, gloving, lab coats, lead aprons were working. I had a lot of fun with this. Because I understood radiation better than most people in the lab - these were tools for biological assays after all - I generally took responsibility for handing clean up and waste disposal and I used this experience to learn a lot about contamination and decontamination, which proved useful throughout my career. (If one iodinates proteins in one's skin, one cannot wash it off of course, which is why gloves were always worn, but even these were never 100% effective.)

Of course, working with radioiodine - which is immediately detectable - is good practice for working with nasty metals, like, as is discussed in this paper, lead, which is not immediately detectable and thus is in many ways worse. The same is true of say, Covid-19 viral particles. I would recommend that anyone who is wearing gloves in situations of possible Covid exposure including exposure in the general public and who has not be trained in contamination and decontamination, take a good look at the figure I will post below.

It should be obvious that we have failed miserably to prevent the contamination of the entire planetary atmosphere with carbon dioxide (and for that matter aerosols of the neurotoxins lead and mercury released in coal burning) but that hasn't prevented humanity from doing the same thing over and over again and expecting a different result. Here I am referring to the quixotic effort to displace fossil fuels - although the focus has often drifted into a stupid and frankly dangerous effort to displace infinitely cleaner nuclear energy rather than fossil fuels - with so called "renewable energy," the most popular form being "solar energy."

The failed effort to address climate change with solar energy hasn't lacked for ever more elaborate schemes, and frankly, although I deplore the solar energy industry in general because of its most dangerous feature - it doesn't work to improve the environment - some interesting science has nonetheless resulted from the huge expense, some of which, unlike the solar industry itself, may someday have practical import.

The latest fad in solar research is in the area of perovskites, solids having the following molecular structure:



(This cartoon is found on the web pages of the Cava Lab at Princeton University.) One can see that these are octahedra embedded in cubic structures.

The most famous of the perovskites in the endless and continuously failed quest to make solar electricity produce energy on a scale that is meaningful are ternary compounds of cesium, iodine and lead. (Sometimes the cesium can be substituted with small organic ions.) There are actually people who believe that distributing lead for "distributed energy" would be a good idea.

I'm not kidding. The rationale is that "it's not as bad as coal burning" or "it's not as bad as car batteries" which is like saying "breast cancer is not as bad as pancreatic cancer."

Go figure.

Laboratory research is often dangerous and I know from experience that people can get quite cavalier about it. It's a bad idea to get cavalier. People's health can be impacted by the reagents with which they work.

Hence this paper is quite a useful reminder that, um, playing with lead base perovskites can be bad for you.

Sustainable Iron-Making Using Oxalic Acid: The Concept, A Brief Review of Key Reactions...

The paper I'll discuss in this post is this one: Sustainable Iron-Making Using Oxalic Acid: The Concept, A Brief Review of Key Reactions, and An Experimental Demonstration of the Iron-Making Process (Phatchada Santawaja, Shinji Kudo,* Aska Mori, Atsushi Tahara, Shusaku Asano, and Jun-ichiro Hayashi, ACS Sustainable Chem. Eng. 2020, 8, 35, 13292–13301)

There's a rumor going around that coal is dead, often accompanied with the delusional statement that so called "renewable energy" killed it. These statements are Trump scale lies. In the 21st century, has coal proved to be the fastest growing source source of energy, growing in terms of primary energy production by more than 63 exajoules from 2000 to 2018, faster than even dangerous natural gas, which was the next fastest growing source of primary energy, having grown by 50 exajoules from 2000 to 2018, roughly 700% percent faster and 600% faster than so called "renewable energy" in this period, ignoring biomass combustion, and hydroelectricity, the former being responsible for about 1/2 of the six to seven million air pollution deaths each year, the latter having destroyed pretty much every major riverine system in the world.

2019 Edition of the World Energy Outlook Table 1.1 Page 38] (I have converted MTOE in the original table to the SI unit exajoules in this text.)

One of the reasons that coal has grown so fast in this century is that poor people around the world - who basically we pretend don't exist - have not agreed to remain desperately impoverished so rich people in the post industrial Western world can pretend that their "Green" Tesla electric cars are powered by solar cells and wind turbines.

It would be a gross understatement to say that I am "skeptical" that so called "renewable energy" will do anything at all to address climate change. Half a century of cheering for it has done zero to prevent California, Australia, and indeed even the arctic from catching fire.

My least favorite form of so called "renewable energy" is represented by the wind industry, and one of my biggest criticisms of this benighted industry is its high mass intensity, particularly with respect to its high steel requirements, coupled with the short life time on average of wind turbines, typically well under twenty years.

There is essentially no steel that is not made on industrial scale with coal, today: Coal fires convert anthracite coal into coke, with the coke being used to reduce iron, alloying it with carbon, to make steel.

That's a fact. Facts matter.

Even if no energy were produced using dangerous fossil fuels - the use of which is rising, not falling - the problem of steel would remain, although it is possible that we may, to some extent, enter the age of titanium, are well into the age of aluminum, but the electrochemical reduction of both of these metals depend on carbon electrodes made from dangerous fossil fuels, coal coke and petroleum coke respectively.

This dependence is why this paper caught my eye.

From the introduction: