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Photon lights a path towards a nuclear clock

From this week's Nature News: Photon lights a path towards a nuclear clock


A long-sought photon that is emitted by the nucleus of a thorium isotope has now been observed. The feat is a key step in efforts to build a nuclear clock, a device that is precise enough to probe the Universe’s best-kept secrets.

I'm not sure if it's open sourced, so some text:

The most precise timekeepers today are atomic clocks, which measure time using the frequency associated with transitions that electrons make between the different energy levels of an atom. But atomic nuclei make similar transitions, and these jumps could potentially offer an even better way of keeping time. In particular, the nucleus of the isotope thorium-229 undergoes a transition with an energy and a frequency that make it uniquely suitable for very precise timekeeping. But observing this transition and identifying its energy precisely are difficult tasks. Writing in Nature, Kraemer et al.1 have detected the photon that is emitted in this transition, an advance that is crucial for the development of nuclear clocks.

Originally discovered in a mineral found off the Norwegian coast in 1828, thorium is named after Thor, the Norse god of thunder. It would take another century and a half for scientists to determine that one specific thorium isotope displays an anomaly that sets it apart from the rest2 — and perhaps makes the element worthy of its other-worldly name. The thorium nucleus in question has 229 nucleons (protons and neutrons), and can transition to an excited state that is only around 8 electronvolts more energetic than its lowest energy (ground) state. This difference is so tiny by nuclear-physics standards that the two states could barely be distinguished when they were first reported2. And it is the transition between these states that could make extraordinary nuclear timekeeping possible.

The working principle behind the nuclear clock closely resembles that of its atomic siblings3. The idea is that a light wave can induce a nucleus to jump between energy levels; the light’s frequency simply must precisely match that corresponding to the energy difference between the levels. This can be achieved with a laser, and — for optimal timekeeping — the ratio between the tuning range (the band of frequencies that can drive the jump) and the transition frequency itself should be very small. For thorium-229, this ratio is minuscule, and the transition is also better protected against stray photons that could affect the signal than are atomic transitions. Unfortunately, the laser required to drive the thorium-229 transition is yet to be built, in part because the exact value of the nuclear-transition energy was, for a long time, not known4–6...

The full original paper is here: Kraemer, S., Moens, J., Athanasakis-Kaklamanakis, M. et al. Observation of the radiative decay of the 229Th nuclear clock isomer. Nature 617, 706–710 (2023).

Thorium-229 does not occur naturally on Earth - it's part of the extinct Cf-249/Np-237 decay chain - but is obtained at Oak Ridge National Laboratory as a decay product of Uranium-233, chiefly to provide the next decay product, actinium-225, an important medical isotope for treatment of cancer using DOTA pay load complexes bound by a linker to cancer targeting antibodies. Oak Ridge has the world's largest supply (by far) of U-233 as a result of the famous MSRE (Molten Salt Reactor Experiment) conducted in the 1960s, and now generating substantial interest. (The Chinese recently built an MSR essentially the same as the MSRE.)

I trust you're having a pleasant holiday weekend.

A Very Wonderful Open Chemical Review On A Most Powerful Analytical Chemistry Tool: IMS/Mass Spec.

In recent years, near the end of my life, I've been overwhelmed with the power of mass spectrometry.

When I was a kid, I was an NMR kind of guy. I have nothing bad to say about NMR, but it can't match the speed and power of mass spectrometry.

In recent years, I've been an advocate for coupling ion mobility with mass spectrometry, and the manufacturers of these instruments are making more and more and more sophisticated instruments to do this.

For anyone interested in this topic who has a modicum of scientific training, I recommend this review, which is open sourced and available to the public without subscription: Ion Mobility Mass Spectrometry (IM-MS) for Structural Biology: Insights Gained by Measuring Mass, Charge, and Collision Cross Section, Emilia Christofi and Perdita Barran, Chemical Reviews 2023 123 (6), 2902-2949.

It's only in the last decade that I became aware of ion mobility experiments, and I thought that the technique was kind of "new."

What I didn't realize, but learned from the article is that historically ion mobility experiments, like mass spectrometry itself, was first explored in the early 20th century, an outgrowth of the then new field, atomic physics, which came after the atomic nature of matter was first understood and finally, after some struggle, universally accepted.

It's a cool article, available electronically, and one does not need to read it all, but can just jump around to the sexy parts.

Have a happy holiday weekend.

Some Interesting Remarks on Lithium Ion Batteries and Magic Recycling Fantasies.

The paper I'll briefly excerpt and on which I'll briefly comment in this post is this one:

Mechanistic Study of Lithium-Ion Battery Cathode Recycling Using Deep Eutectic Solvents Salma H. Alhashim, Sohini Bhattacharyya, Raphael Tromer, Ahmad Kabbani, Ganguli Babu, Eliezer Fernando Oliveira, Douglas S. Galvao, and Pulickel M. Ajayan ACS Sustainable Chemistry & Engineering 2023 11 (18), 6914-6922

It begins with a nonsense statement, this one:

Lithium-ion batteries (LiB) are crucial in the move toward a net-zero carbon emission economy...

It's depressing to see a clear statement of ignorance of the 2nd law of thermodynamics in a scientific journal: Storing energy wastes energy, specifically primary energy. Since we don't have clean primary energy, except in the stupid fantasies of people who are apparently unacquainted with numbers - numbers don't lie - storing energy makes things worse not better.

The authors might be excused as this is a rote statement in an oblivious culture of denial.

(I've written so many posts here, I cannot even come close to remembering many of them, but one of my favorites, about batteries, which I've actually bookmarked, is here: The Number of Tesla Powerwalls Required That Would Address the Current German Dunkleflaute Event.)

We have battery morons and hydrogen morons here and all over the world; what we don't have is clean primary energy.
This is because the antinukes won the argument, managed to trash vast areas of the planet with short lived industrial junk they call, oxymoronically, "renewable energy," resulting in us having seen readings for the concentration of the dangerous fossil fuel waste carbon dioxide greater than 424 ppm in the planetary atmosphere, less than ten years after we first saw readings of 400 ppm.

One of the things that hand wavers like to do when presented with the environmental consequences of their fantasies is to chant "recycle." Of course, if the use of a material is growing, this means that more of it is in use, and one cannot recycle what is in use. It also matters what the volume and more importantly the geographic distribution of the purported recycling scheme will be. It costs energy to collect diffuse materials which is why magic plastic recycling has proved to be disastrous failure.

Anyway, the paper cited is about a new magic recycling scheme, but the text is interesting because it demonstrates under current conditions how difficult and more importantly how dirty current recycling of lithium batteries really is.

Lithium-ion batteries (LiB) are crucial in the move toward a net-zero carbon emission economy and have been of great importance in defining national and international energy policies. (1) Globally, the use of LiBs is projected to increase by almost three folds from 250 million units in 1998 to 700 million units in 2030. (2) This in turn has culminated in the double-edged problem of LiB waste management on one hand and supply of critical materials (e.g., cobalt, nickel, graphite, lithium, and manganese) on the other. These essential materials have limited reserves, many of which lie in conflicted regions and war zones. Considering the current trends in mobile and stationary LiBs usage, the demand for graphite, lithium, and cobalt is expected to increase by almost 500% by 2050, whereas a shortage of nickel is estimated to arise within the next five to six years. (3,4) Additionally, the increase in the use of LiBs also results in a huge amount of battery waste (∼330 kt only in 2020). (5) Most of this ends up in landfills, thereby causing irreparable harm to the environment. Thus, the recycling of LiB systems is a one-stone-two-bird approach that reduces environmental hazards while establishing a circular green economy, diminishing the need for extensive mining. The most commonly prevalent methods of recovering the active metals from LiB cathodes include pyrometallurgy, (6,7) hydrometallurgy, (8,9) bioleaching, (10,11) and mechanical methods. (12) Among these methods, pyrometallurgy is widely used in industries, in spite of the very high energy requirements and environmental concerns due to hazardous gaseous emissions. Additionally, the resultant mixed slag from this process makes it extremely difficult to recover Li effectively. While hydrometallurgy ensures very high leaching efficiencies at relatively low temperatures, the reagents involved are often highly corrosive concentrated inorganic acids, e.g., nitric, sulfuric, or hydrochloric acids, posing a threat to the environment and workers. On the contrary, bioleaching involving the recovery of cathode metals using organic and inorganic acids produced from the microbial activity is environmentally benign but with poor efficiencies. Thus, it is important to strike a balance between environmental sustainability and leaching efficiencies (LE) in order to establish a commercially viable recovery system. Recently, the use of deep eutectic solvents (DES) in leaching spent LiB cathodes has improved the hydrometallurgy process by introducing an efficient and environmentally benign solution to the problem. (13)...

The authors then go into a discussion of deep eutectic solvents, the usual stuff, in this choline chloride based solvents.

None of this is involved with the energy cost of merely collecting 700 million lithium batteries of course.

The mass of lithium batteries is mind boggling. Just as climate change is accelerating because of nonsense beliefs that batteries (or worse, hydrogen) can save the world, so is the risk of distributed material pollutants is accelerating.

Happily there is an upper limit on how many batteries can really be made, determined, as the paper notes, but limits in the supplies of Nickel - largely obtained in very dirty Russian mines in Siberia - and cobalt, mined by de facto slaves in Africa.

One should note that I favor the recycling of used nuclear fuels, but these are small in volume and mass, and generally located in centralized areas, the plants where they are generated. Recycling used nuclear fuels is not risk free of course, but as in all things nuclear compared to all of the rather stupid popular stuff, as in "batteries will save us," this when we don't have clean energy and aren't even remotely close to having it, the risks of recycling nuclear fuel are dwarfed by the risks of not recycling it.

Have an enjoyable holiday weekend.

I've been writing here through the accumulation 50 ppm of the dangerous fossil fuel waste CO2 in...

...in the planetary atmosphere, in units of time, and not CO2 accumulations, about 20 years.

Over those 20 years, I've heard endless "percent talk" from advocates of so called "renewable energy" who want to define whether or not it is required to endorse this bullshit fantasy in order to be a member of the Democratic Party.

They come and go, like the wind, like the sunrise and the sunset.

I'm not a Democrat because I endorse cute, quaint, but extremely myopic consumer car cults, including the worthless hydrogen and battery fantasies, with specious uncritical uneducated blather. I'm a Democrat because I believe in human rights, because poverty matters to me, because I despise racism and because, unlike many blathering fools, I care deeply about the environment.

I was a Democrat before the founding of the International Journal of Hydrogen Energy in 1976, which has been publishing articles about a putative "hydrogen economy" for 47 years, even though it didn't arrive, isn't here, and because it requires ignoring engineering and science to make it a reality, will never be viable.

Forty seven years of chanting about hydrogen has not made it worth a damned thing.

Of course, the people hyping this crap, continuously posting cheap commercial advertising to raise more money to waste on fantasies, are disinterested in physical laws, and the engineering and science that depend on them, and are completely disinterested in climate change, except to offer disingenuous and dishonest apologetics to attempt to conceal their disinterest in the subject.

Now, of course, the people who carry on with this purely defensive posture to divert attention from their disinterest in climate change wouldn't know, and don't care, that in 1976, when the first edition of the Journal of Hydrogen Energy was published, the annual average concentration of the dangerous fossil fuel waste on this planet was 331.03 ppm, and as of yesterday it was 92 ppm higher.

May 24: 423.70 ppm
May 23: 423.87 ppm
May 22: 424.23 ppm
May 21: 423.74 ppm
May 20: 423.79 ppm
Last Updated: May 25, 2023

Recent Daily Average Mauna Loa CO2

People who don't give a rat's ass about climate change, who just want to gaze admiringly at marketing videos of prototypes of consumer junk that will not matter to the more than 2 billion people on this planet who lack access to decent water don't look at numbers. I expect that they are incompetent to understand them, but at the end of the day, I really don't care what they think. I work at my ideas. I'm not admiringly gazing at cartoons.

Now as it happens, people who blindly and foolishly worship the wind and solar junk that has done nothing to address climate change love to cite their fellow scientific illiterates, journalists in our "but her emails" media often claiming, despite oodles of data, that solar and wind are "cheap."

Since they do not take time to read at a deep level, a level beyond comic books, they may not have a clue on how much money was spent on solar and wind junk in this century.

Since I do read on a deep level, I have that referenced data at my fingertips:

In the 21st century, we spent, invested on this reactionary fantasy, more than 3.3319 trillion dollars on solar and wind junk, almost all of which will be landfill in about 25 years. (The number 3.3319 trillion dollars refers to the period between 2004 and 2019 inclusive.)

Source: Global Trends in Renewable Energy Investment 2020 (Figure 42, page 62).

Fifteen years, more than 3 trillion dollars spent on comic book level wishful thinking and delusion, this on a planet where 2 billion people don't have clean water, people who couldn't give a rat's ass about marketing videos of Potemkin hydrogen stations in China for cute demo hydrogen trucks, and here's where we are: In 2004, when we were convinced to embrace this trillion dollar reactionary scheme to return to the early 19th century, the mean average concentration of dangerous fossil fuel waste was 377.30 ppm.

How do I define worthless? I have no apologies for stating clearly, unambiguously, without reservation that for energy systems, those which fail to address human needs, which fail to protect the environment, that do nothing more than soak up money to satisfy the tiresome reactionary daydreams of the poorly educated bourgeoisie are, just that, worthless.

The data is in for 2021 on how much energy this worthless junk produced after soaking up trillions of dollars, not even counting the cost, environmental, economic and health of the required redundancies.

Source: 2022 IEA World Energy Outlook Table A 1a, page 435

After 50 years, half a century, of mindless cheering, the entire combined solar and wind industry at 12 Exajoules built at these trillion dollar rates, was not even able to cover the increase in the use of dangerous natural gas, coal and oil - the source of the bulk of the world's hydrogen by the way - from 2020 to 2021, an 11 Exajoule increase for dangerous oil, a 7 Exajoule increase for dangerous natural gas, and an 8 Exajoule increase in the use of dangerous coal.

Now dumb journalists and the people who cite them like to pretend like to pretend that the solar and wind industries are about dangerous fossil fuels, but clearly they aren't. Journalists in the "but her emails" media can lie all they want - and they do lie all they want - but numbers don't lie.

Twelve Exajoules of energy per year at a cost of over three trillion dollars spent on consumer junk that will need replacement every twenty years has nothing to do with my Democratic values. For me the Democratic Party that I have supported for over half a century was never about endorsing dogmatic cult thinking, even when it's popular but pernicious, particularly consumer cult thinking, "Look at my car! Look at my truck," bullshit.

The planet is on fire. Clearly there are people who don't give a shit about that, and like Repukes, they feel that they have the right to criticize those who do care, and care a great deal.

There is worthless junk and there are worthless people; in general they tend to be linked to one another.

Once again, let me make this clear in case anyone missed it: Numbers don't lie. People lie, but numbers don't.

Have a nice day tomorrow and enjoy the holiday weekend.

Someone should ask the ANS if the National Organization for Women Should Invite Brett Kavanaugh...

...to speak at one of its convocations on women's rights.

I'm not a member of the American Nuclear Society - I'm not a nuclear professional although I am a nuclear advocate - but I am on their mailing list and their news feeds. (If free, I view a few their webinars when available.)

They've sent me an ad for their annual convention telling me that I really need to hear from the speakers at the convention, including this guy, Ed Lyman at the Union of Concerned "Scientists."

Ed Lyman, often identified by himself, his benighted organization, and our "but her emails" media as a "nuclear non-proliferation expert."

Ed is very, very, very, very "concerned" about used nuclear fuel and often writes papers like this piece of tiresome nonsense filled with conditional words like "could" along with the usual appeal these people make about "terrorist attacks."

Thus, although the NRC backfit analysis found that the huge quantity of fission products released by a dense-packed pool fire could be dramatically reduced by lowering the fuel density, it estimated that the probability of a fire resulting in a large release would be small—on the order of 4 × 10−6 per pool per year, although with a large uncertainty (7 × 10−7 to 3 × 10−5).

The NRC's cost-benefit analysis did not account for the possibility of a terrorist attack, which cannot be quantified but should not be ignored (7). In addition, the NRC made a series of assumptions that tended to minimize the estimated health and economic consequences of a high-density release. After making these assumptions and ignoring uncertainties, the NRC found that the probability-weighted benefits to the public from transferring spent fuel to passively air-cooled dry cask storage did not justify the estimated cost of $5 billion to the nuclear utilities (about $50 million per reactor).

A recent National Academy of Sciences study (on which author F.v.H. served) found that the NRC cost-benefit analysis—unreasonably, in our view—excluded accident consequences beyond 50 miles and underestimated consequences in a number of other ways (4). In response to a petition by the state of New York, the NRC acknowledged that its assumption in such calculations, that virtually all the relocated population could return home within less than a year, was inconsistent with the experience in Japan, where some of the relocated population is just beginning to return after 6 years...

He concludes with a series of other "coulds" and "ifs:"

If a spent fuel–pool fire were to occur, however, under the Price-Anderson Act of 1957, the nuclear industry would be liable only for damages up to $13.6 billion, leaving the public to deal with damages exceeding that amount (15). A fire in a dense-packed fuel pool could cause trillions of dollars in damages (9).

To reduce the risk and invest in infrastructure, Congress could consider allocating $5 billion for casks to store spent fuel. The federal government is already reimbursing nuclear utilities almost $1 billion per year for casks needed to store older spent fuel because the Department of Energy has not fulfilled its commitment to remove the fuel to an underground repository or interim storage site (16, 17). States also could act to reduce the risk. As part of its policy to reduce fossil fuel use, New York recently decided to mandate subsidies totaling about $500 million per year for continued operation of four nuclear power reactors (18). Illinois has adopted a similar policy, and other states are considering the same. States could condition such subsidies on agreements by utilities to end dense-packing of spent fuel pools.

Nuclear safety regulation in the post-Fukushima era SCIENCE
26 May 2017 Vol 356, Issue 6340 pp. 808-809.

Now one can ask about how many lives would be saved by these expenditures which Ed recommends. How would it compare to lives saved by spending the same amount of money on providing clean sanitation to those who lack it?

But Ed is spectacularly un"concerned" with the cost of poverty; we should rather address his concerns that something that doesn't happen could happen.

We also could see 500 ppm concentrations of carbon dioxide, dangerous fossil fuel waste, in the planetary atmosphere, in the lifetimes of people now living. Hell, I'll do some soothsaying and suggest we will see 500 ppm concentrations of fossil fuel waste before we see that big, bad, used fuel fire that Ed and Frank love to muse about.

Now, in dealing with mindless antinukes here who whine about so called "nuclear waste," I have taken to asking them to show, that after 70 years of the accumulation of used nuclear fuel on this planet, if anyone of them could show that this accumulation has killed as many people as will die in the next six hours from air pollution.

That would be over 4500 people: Global burden of 87 risk factors in 204 countries and territories, 1990–2019: a systematic analysis for the Global Burden of Disease Study 2019 (Lancet Volume 396, Issue 10258, 17–23 October 2020, Pages 1223-1249).

Usually the refuse to answer the question, either by offering insipid childish conditions, changed subjects, or simply by slithering away unashamed with their indifference to human life.

Let's be clear about "Ed Lyman" "Expert." Ed is very "concerned" about used nuclear fuel, which has a spectacular record of not killing anyone, but he doesn't give a flying fuck about 42 million people who died from air pollution since he wrote about this "could" trillion dollar bullshit. He is not "concerned" about how many people are killed by climate change, which is dangerous fossil fuel waste, or air pollution, both which has an odious record of killing people continuously without stop.

He's not "concerned" about the cost of climate change, the tremendous costs of extreme weather, the associated disability and deaths its caused. This, Ed, is not a "could" scenario. It's an IS scenario, not a "could" scenario. People are dying right now while you whine about used nuclear fuel.

As he's "concerned" about Fukushima, he ought to have the human decency to compare the number of deaths from radiation in the event with the number of people killed by seawater.

But Ed is not "concerned" with the safety of coastal cities. They don't matter, and the trillions of dollars associated with the damage done to them because of climate change is of no concern to him.

As for terrorist events, Ed is not calling for a vast expenditure on preventing fossil fuel terrorism - he seems spectacularly disinterested in the fossil fuel powered terrorists who struck two buildings in New York causing them to collapse from burning jet fuel - the terrorists in question a collection of people who came of age in an oil producing state, Saudi Arabia.

Ed's not "concerned" with observed fossil fuel terrorism.

What is his proposal for "building safety" in light of his complete indifference to fossil fuel terrorism, terrorism that is actually observed. (Tim McVeigh used diesel fuel and fertilizer obtained from natural gas to commit his act of terrorism, well before the World Trade Center attacks.)

He is very concerned about nuclear war, but not about the people who die in oil powered wars, like those poor people dying right now in Ukraine because of the use of fossil fuel based weapons funded by fossil fuel sales to a prominent antinuke nation, Germany.

In fact, in this century, it is claimed that the death toll from wars using fossil fuels diverted to weapons of mass destruction is just shy of one million people, from just five wars, Iraq, Afghanistan, Syria, Yemen, and Pakistan. This is about 10 Hiroshima's and Nagasakis, and although I'm sure that Ed and Frank are ready with all kinds of "coulds" and "ifs" the number of people killed in nuclear wars since 1946, about 3/4 of a century, is zero.

Again, I have no rights to comment on decisions of the ANS to invite people whose selective attention quite literally kills people, in vast numbers. I'm not a member, and I don't attend its scientific sessions.

But it strikes me that inviting Ed Lyman, consummate expert in engaging in selective attention, to speak at an ANS meeting is like inviting Ron DeSantis to speak at a meeting of the NAACP, or a convention of educators.

I hope the audience views him with the same disgust that I do.

He's an awful, toxic fool.

TVA CEO Says Building One New Nuclear Reactor Is a Bad Idea. He'd Rather Build 20 Reactors.

TVA Head Wants Nothing to Do with Building One Reactor Unless He Can Build 20

Building a nuclear power plant is a difficult job. It takes years of planning and sometimes more than a decade to complete. The risk of schedule delays is great, especially on first-of-a-kind projects, and the financial implications of such setbacks can ruin a company.

Yet, the Tennessee Valley Authority’s (TVA’s) president and CEO, Jeff Lyash, suggested the risk is worth taking, that is, if lessons learned from one project can be parlayed into success in future projects. That’s why TVA is studying the addition of a small modular reactor (SMR) at its Clinch River site. Lyash envisions using that first unit as a template to eventually make Clinch River a four-unit site, and then replicating that design in at least four other locations within TVA’s service territory.

“I’ve said very vocally, I [want] nothing to do with building one reactor, unless I can build 20—and 20 is the low estimate—and so, this is what Clinch River is about,” Lyash said as a guest on The POWER Podcast.

While TVA continues to support and examine all of the various SMR designs being proposed, and it is also following the development of Generation IV advanced nuclear technology, it has selected GE-Hitachi’s (GEH’s) BWRX-300 design for its Clinch River site. “We picked the BWRX-300 technology because the X stands for the 10th generation. We know this fuel works. We know this technology works,” Lyash said.

Lyash noted that there are 50 years’ worth of experience behind the GEH design. He said engineers have applied modularization processes and advanced manufacturing techniques to advance the design, but the technology behind it all is well-established...

...Because of TVA’s unique position as an entity of the federal government, Lyash believes it should be a leader for the power industry. “Because of TVA’s special role, we’re really doing it to support the nation, because what we’d really love to happen is fast followers,” he said. In other words, he hopes once TVA proves that an SMR can be constructed on time and on budget, other power companies will jump on the new nuclear construction bandwagon.

In March, TVA signed a technology collaboration agreement with Canada’s Ontario Power Generation (OPG) and Synthos Green Energy (SGE), which is part of Poland’s biggest private industrial group. The deal is intended to shape a standard design for the BWRX-300, which could speed up the technology’s regulatory acceptance and spur future deployments. “My view from the beginning is: this is best done in partnership, and it’s best done that way because, again, we’re not trying to build one reactor and we’re not trying to just do it for TVA,” Lyash said...

... Poland, meanwhile, is one of the most carbon-intense nations in Europe, so it is keen on adding nuclear to decarbonize its power supply. Therefore, partnering with SGE made a lot of sense to Lyash. “That represents an international market,” he said. “Why is that important? Well, if you’re going to scale this, you have to scale it. You have to have a book of business. You have to have owners who are willing to build so that you get the investment in the supply chain and the workforce development to do it...”

I very much like this thinking; building back better nuclear manufacturing infrastructure by bootstrapping up. It's similar to an idea I've been nursing, using used nuclear fuel on site to build a small reactor to power electrorefining of the all the additional fuel to build a series of breed and burn reactors on site without any dependence on mined uranium (or thorium).

This news item is not all good news. TVA also plans to squander money on solar installations, a very bad idea when compared to 20 nuclear reactors, throwing good money after bad.

The Difference Between Thermodynamically Rich Heat and Heat as a Thermodynamic Degradant.

In a PM a correspondent here at DU wrote me thus:

what you mean by "Heat is the least thermodynamically degraded form of energy." (Point me to some text rather than explain if you wish.) You compare electricity to heat in another part of the post. I took three semesters of undergraduate physics, one being mostly thermo, and even taught a semester of P Chem, but my immediate puzzle is that I see heat as being both the source of useful energy if you have a lot (from nuclei or reduced carbon) and the useless end point ("heat death" back when) when its entropy is high. Do you mean that electricity is only a step along the way from low entropy/high G to a high entropy/low G state?

I actually never got around to answering the question, but was reminded of it when I came across this paper recently:

Solvent Effect on the Chemical Equilibrium of Ammonium Carbamate for Chemical Heat Pump Suzhou Dai, Yonggao Yin, Yikai Wang, Xuanlin Liu, Maurizio Peruzzini, and Francesco Barzagli Industrial & Engineering Chemistry Research 2023 62 (18), 7212-7223.

The device described in this paper is kind of a heat pump on steroids; it uses both compressional heat and the heat of chemical reactions to upgrade low grade heat to high grade heat, but to do this, it requires work, the expenditure of energy.

But let's cut to the chase. The correspondent is right about what I mean in the last sentence. It is fairly straight forward to show why this is true, if one understands that one statement of the second law of thermodynamics is "every process by which one form of energy is converted to another form will result in an increase in entropy," thus a loss of irrecoverable energy to the environment.

Before proceeding to the simple example, a little bit about entropy, what it is.

In general, the the increase in entropy is observed in the form of heat energy, although entropy can take other forms.

We are all familiar with irreversible processes. If we drop an egg off a table, it falls and breaks into pieces and goo. We never observe pieces and goo reassembling into the form of an egg. The shattering of the egg is an example of entropy. The development of statistical mechanics allowed Boltzmann to define what entropy is on a molecular scale, but before that, before Boltzmann entropy was known by the Clausius inequality:

The funny looking "delta" in the equality refers to the fact that this is an inexact differential; the way it integrates depends on the path. q is the standard variable used to describe heat, and S is entropy. If the equality holds rather than the greater than symbol, the process is reversible, but reversible processes in thermodynamics are idealized forms; they do not exist in real life.

As the nature of heat, then something of a mystery, was explored in the 19th century, largely the result of the invention of heat engines, in particular the steam engine, people realized that if you run a locomotive backwards, it never sucks all of the smoke back into the smokestack and reassemble the lumps of coal after sucking heat out of the environment. The locomotive is like a smashed egg. Clausius, writing in the middle of the 19th century - just as humanity was abandoning reliance on the weather for energy for a reason - basically was the first person to define entropy per se, building on the more intuitive work of the French engineer Carnot.

One does not need to have anymore than a knowledge of 7th grade algebra to see intuitively by looking at the Clausius inequality that a way to minimize entropy is to have the transfer of heat (by any path) is to do it at high temperatures. Thus having high temperatures is a route to minimizing entropy.

Now we are in a position to describe by example - I've done this before in this space - why I say electricity is thermodynamically degraded.

All heat engines of course run on primary energy. In a filthy dangerous fossil fuel plant this primary energy is the potential energy in the dangerous fossil fuel, coal, oil, or gas, but in order to recover this potential energy we combust the dangerous fossil fuel to make heat. Chemical energy is converted to heat energy. In a clean nuclear plant, the energy comes from the nucleus of a fissionable atom, usually uranium or plutonium, although neptunium, americium and curium would work too. Nuclear energy is converted to heat energy.

The common element is heat. Now let's look at the conversion of this common form of energy heat, and see what happens in making it into electricity, and moreover in storing it. The heat of the fuel is converted into steam energy (pressurized gas) at a thermodynamic loss - the boiler radiates heat to the environment. The steam is converted to mechanical energy at a thermodynamic loss, friction in the turbine, heat radiating from the housing. The mechanical energy is converted to electrical energy using a generator at a thermodynamic loss, friction, resistance in the copper wire, air resistance in the armature, etc. The electricity is then "shipped" (transported) over wires at a thermodynamic loss, the heat of electrical resistance.

Thus the electricity is thermodynamically degraded. Heat is converted to steam, steam is converted to mechanical energy, mechanical energy is converted to electrical energy, electrical energy is transported, four steps, each surrendering some of the value of the original heat to electricity.

A Rankine cycle (steam) power plant runs about 33% efficiency on average, depending on the temperature of the steam as well as the temperature of the surroundings: Powerplants are more efficient in winter than in summer. Thus right out fo the box, about 67% of the energy is wasted in just this step, steam to mechanical energy. This is really not surprising, there are lots of opportunities for steam to reject heat to the environment in these processes.

Now lets consider what happens in some of the more stupid fantasies that run around, batteries and hydrogen. The already thermodynamically degraded electricity is converted to chemical energy in the battery at a thermodynamic loss; most people can observe that lithium batteries get warm when they recharge; indeed under some conditions they'll burst into flame. Some of the stored electricity is degraded over time whether the battery is used or not, via internal diffusion. However, if the battery is used to provide electricity, chemical energy is converted back to electrical energy at a thermodynamic loss. If the electricity is used to drive a motor, the electrical energy is converted to mechanical energy at a thermodynamic loss. Four steps have now become (for an electric car) 7 steps. (It is true that mechanical energy can be converted back into chemical energy by electronic braking, but in this case 7 steps have become 9.)

Hydrogen is even worse, because in general, the hydrogen gas has to be compressed, and if liquified, cooled below its critical temperature, involving a huge amount of work (energy).

Almost all of the energy processes described release energy as heat, low grade heat. Low grade heat can be - often wisely - upgraded to high grade heat with heat pumps, but this also expends energy. Some heat pumps are better than others. The ammonium carbamate heat pump described in the paper referenced above is one that is new to me; on some level it should have been obvious, but I never thought of it. Industrially ammonium carbamate is a rather important compound, a key intermediate for example of some routes to urea for fertilizer and for SCR catalysts for diesel engines. Ammonium carbamate is synthesized by reacting ammonia gas with carbon dioxide gas under pressure. Both ammonia and carbon dioxide have been used as refrigerants, this process adds a little extra "kick" to their efficiency, but the second law of thermodynamics still applies to the system; it requires energy inputs to run, just like any other refrigerator.

It follows from the above that the most sensible way to store energy - if one must do so for load leveling for example - is as heat. Batteries and hydrogen are the worst, and most wasteful ways to store energy. I note that the direct conversion of heat to chemical energy, eliminating the degradation associated with electricity, is a thermochemical process. These are known, my personal favorite being the much discussed SI (sulfur iodine) cycle. There are others.

Have a nice day tomorrow.

Mauna Loa CO2 Observatory Milestone. Ten years ago this week we first saw readings above 400 ppm.

It may be true that the annual peak in CO2 concentrations at the Mauna Loa (Maunakea) CO2 observatory may have passed in the week of May 7, when the reading came in at 424.24 ppm. It is possible it will be passed later this month, even early June.

Last week's readings are these:

Week beginning on May 14, 2023: 423.50 ppm
Weekly value from 1 year ago: 421.20 ppm
Weekly value from 10 years ago: 400.14 ppm
Last updated: May 21, 2023

Weekly average CO2 at Mauna Loa

This reading, 400.14 ppm was the first to exceed 400 ppm, in the week May 19, 2013.

On average, a one year running average of ten year comparators of weekly data is higher than this single data point represents; it is currently coming in 24.26 ppm/10 years. (Except for the last few weeks, 2023 has been a relatively mild year; for the week of Jan. 1, 2023, this running average was 24.50 ppm/10 years; the data is noisy.)

The first reading to exceed 420 ppm was in the week beginning April 24, 2021, when the reading was 420.01 ppm, representing the peak reading in 2021. Last year's maximum came in at 421.63 ppm for the week beginning May 29, 2022.

The first reading to exceed 380 ppm was in for the week beginning April 4, 2004.

Between 2004 and 2018 the amount of money squandered on solar and wind energy amounted to over three trillion dollars, $3,062,600,000,000 according to the Frankfurt School UNEP 2020 report (see figure 42).

In recent times, the point of the solar and wind energy has been described as being about addressing climate change. As someone who has followed this obscene waste of money for decades - I even once supported it - I know that this is nonsense. It never was about climate change. The main point of the industry was never about addressing dangerous fossil fuels. It was always about attacking nuclear energy. The Germans didn't phase out coal; they embraced it as a result of embracing solar and wind energy. They phased out nuclear energy. The attack on nuclear energy was successful, with the result that climate change is destroying the planet.

Here we are, in a year that we first saw 424 ppm of the dangerous fossil fuel waste carbon dioxide in the planetary atmosphere. The planet is on fire. I would have thought that the people who are responsible for this might have considered whether climate change is "too dangerous," but their definition of "too dangerous" was applied with extreme ignorance producing a very malign result.

If I sound angry, it's probably because I am.

I trust you're having a pleasant weekend.

Produced Fracking Water Disposal in California Inputs Selenium and Arsenic in Surface Acquifers.

Regrettably I can't spend much time with this paper here: Historic and Contemporary Surface Disposal of Produced Water Likely Inputs Arsenic and Selenium to Surficial Aquifers, Robert J. Rossi, Rebecca A. Tisherman, Jessie M. Jaeger, Jeremy Domen, Seth B. C. Shonkoff, and Dominic C. DiGiulio Environmental Science & Technology 2023 57 (19), 7559-7567

Text from the introduction:

California was historically, and is currently, one of the largest oil and gas producing regions in the conterminous United States (U.S.). (1) Oil and gas development generates sizable volumes of wastewater (produced water) by extracting waters contained within source formations and/or water used to enhance hydrocarbon recovery, and these waters are known to contain many organic and inorganic contaminants. (2) Multiple strategies have been utilized to dispose of the large volume of produced water generated by oil and gas development processes.

In addition to subsurface injection by injection wells (generally the most common disposal method), in California, produced water has also been disposed of in lined and unlined surface impoundments, hereafter referred to as produced water ponds. (3) Unlined ponds dispose of the produced water via both percolation and evaporation. While the frequency of this disposal method has decreased substantially since 2014, (3) produced water ponds have been heavily utilized since the mid-20th century, and recent work has demonstrated impacts to groundwaters near disposal facilities. (3,4)

The largest number of unlined produced water ponds (at least 1470 active, inactive, or closed ponds) (3) are located in the southern portion of the San Joaquin Valley (SJV), one of the most productive agricultural regions in the world. (5) Due to the arid SJV climate, agriculture in this region is heavily reliant on groundwater resources. (6) However, droughts have generally diminished rates of groundwater recharge while pumping demands have simultaneously increased, leading to an overdraft in areas of the SJV. (7) Thus, decreased recharge and the subsequent reduced dilution of produced water in existing groundwater increase the potential for impact to diminishing groundwater resources...

...Arsenic and Se are geogenic contaminants in the SJV and are commonly detected in SJV produced water ponds. Arsenic is sourced from As-rich strata in both the western and eastern margins of the SJV, whereas Se-rich parent materials are generally found in the western and southwestern margins of the SJV. (10) In the 1980s, high levels of Se in agricultural evaporation pond waters caused the high mortality and deformity rates of waterbirds in the SJV. (11) Arsenic is a notorious groundwater contaminant that can increase the risk of cancer and cause other health effects in humans. (12) About 10% of the SJV wells tested between 2008 and 2018 had As concentrations exceeding World Health Organization recommendations. (6)...

Oh well then...

In California, where the overwhelming source of production of electricity for all that electrified "green" stuff is from dangerous natural gas, nuclear power is considered "too dangerous," but gas is just fine.

The picture presented in this paper, again with which I can spend very little time, isn't pretty, particularly given California's involvement with the food supply, not that the constituents who elected Kevin McCarthy give a rat's ass about health or sustainability since it takes away from their efforts to distribute the resources of the middle class to filthy (literally) rich people.

Don't worry. Be happy.

California is very good at producing "aspirational" laws that everyone ignores, particularly because so many of them have "by xxxx" where xxxx is some year in the future when the people passing the law will have retired or be dead.

From the conclusion:

...Despite the enactment of the Sustainable Groundwater Management Act in 2014, (67−69) which aims to combat overdraft in the SJV, groundwater depletion is still occurring. Specifically, Argus et al. (2022) concluded that the southern SJV lost 1.5 ± 0.4 km3 yr–1 during 2006–2021. (70) Similarly, Liu et al. (2022) observed a decrease in groundwater storage (2.55 ± 0.60 km3 yr–1) in the southern SJV over the present drought (2019–2022). (71) Depleted aquifers will be more sensitive to As and Se contaminant fluxes, and during droughts, any As/Se contamination imparted by produced water disposal will unlikely be diluted by mixing with meteoric or surface waters. Additionally, desiccation of shallow aquifers may create subsurface pools of contamination, comparable to current As challenges facing the SJV. (6) During persistent wet periods, pools of legacy contamination could be remobilized and transported to nearby aquifers if recharge waters are undersaturated in respect to As- and Se-bearing minerals. (72)...

Unh Oh... It appears that efforts to contain the arsenic will mobilize the selenium, and maybe even, (gasp!!!!!!) natural uranium in the California rocks through which ground water percolates.

...If contamination plumes were to merge, mixtures of trace metal contamination could prove exceedingly difficult and expensive to address. For example, As, a relatively common water contaminant in the SJV, is generally less mobile in oxic environments. Thus, injecting oxic waters into aquifers could limit the mobility of As species and address potential As contamination. However, we observe that As often coexists with Se in disposal waters, and as such, this strategy may reduce As mobility while simultaneously facilitating Se mobility. Furthermore, as the valley fill sediments of the SJV are well known to potentially contain U, (76) this hypothetical solution may lead to both Se and U mobilization...

Have a nice Sunday.

Human-evolution story rewritten by fresh data and more computing power

I came across this news item in my Nature Briefing News Feed:

Human-evolution story rewritten by fresh data and more computing power


Humans did not emerge from a single region of Africa, suggests a powerful modelling study. Rather, our ancestors moved and intermingled for millennia.

The widely held idea that modern-day humans originated from a single region of Africa is being challenged. Models using a vast amount of genomic data suggest that humans arose from multiple ancestral populations around the continent. These ancient populations — which lived more than one million years ago — would have all been the same hominin species but genetically slightly different.

The models supporting this theory rely on new software and genomic-sequencing data from current African and Eurasian populations, as well as Neanderthal remains. Researchers published the results on 17 May in Nature1.

The study contributes more evidence to the idea that there is “no single birthplace in Africa, and that human evolution is a process with very deep African roots”, says Eleanor Scerri, an evolutionary archaeologist at the Max Planck Institute of Geoanthropology in Jena, Germany.

The single-origin theory has been popular for decades, partly on the basis of fossil records. But the theory doesn’t fit the data well, says Scerri. All of the tools and physical traits attributed to Homo sapiens cropped up throughout Africa around a similar time, 300,000 to 100,000 years ago. If humans had radiated from a single location, archaeologists would expect to see more recent fossils farther away from a central point, and older ones closer to it...

...This study incorporated genome-sequencing data from existing eastern and western African populations and the Nama people of southern Africa. This spread of genomic data helped the researchers to understand and track the historical movement of genes across generations.

“We really wanted to sit down and very systematically evaluate the models in a more creative way,” says Henn. “It’s a new model for human evolution that is concrete.”

The models used variables such as migration and population merging to predict gene flow over the course of thousands of years. Those predictions were then compared with the genetic variation seen today to determine which models matched the data best...
Ultimately, questions still abound about humans’ origins. Henn wants to add more DNA from other African regions to the models to see if that changes their results. She also hopes to use the data to make predictions about the fossil record, such as what features would be found in human fossils from a particular area...

The full original scientific paper is here:

A weakly structured stem for human origins in Africa

It is said to be open sourced.

For convenience a graphic from the paper, as well as it's caption:

The caption:

a,b, In the two best-fitting parameterizations of early population structure, continuous migration (a) and multiple mergers (b), models that include ongoing migration between stem populations outperform those in which stem populations are isolated. Most of the recent populations are also connected by continuous, reciprocal migration that is indicated by double-headed arrows (labels matched to migration rates and divergence times in Table 1). These migrations last for the duration of the coexistence of contemporaneous populations with constant migration rates over those intervals. The merger-with-stem-migration model (b, with LL = −101,600) outperformed the continuous-migration model (a, with LL = −115,300). Colours are used to distinguish overlapping branches. The letters a–i represent continuous migration between pairs of populations, as described in Table 1.

I recently had a chance to visit the Smithsonian Museum of Natural History in Washington DC. They have a very nice display on human evolution, lots of models of fossils, some actual fossils, videos, etc.

But of course, someone was marching through the (happily) crowded exhibit announcing loudly to her companion that she didn't believe in evolution, the increasingly common claim that facts are subject to belief but religious texts written by ancient barely literate sheepherders were inviolable.

I trust you're enjoying the weekend.

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