NNadir

NNadir's Journal

May 31, 2023

The occurrence of PFAS in landfill gas.

The paper to which I'll briefly refer is this one:

Neutral Per- and Polyfluoroalkyl Substances in In Situ Landfill Gas by Thermal Desorption–Gas Chromatography–Mass Spectrometry Ivan A. Titaley, Florentino B. De la Cruz, Morton A. Barlaz, and Jennifer A. Field Environmental Science & Technology Letters 2023 10 (3), 214-221.

PFAS (Perfluoroalkyl substances) are now ubitiquous, persistent chemicals.

I have written a number of posts in this space on the subject.

One form of so called "renewable energy" - almost certainly more prevalent than solar and wind in terms of energy produced - is the combustion of "waste," typically municipal garbage. However because this, like biomass combustion, is a major driver of air pollution where it is used, the majority of municipal waste is still landfilled, whereby the associated toxicology, like climate change, is dumped on future generations.

On the bright side, or the dark side, depending on how it's used, landfills generate methane gas as waste decomposes. This gas can be and often is combusted in power plants, making landfills slightly less odious.

It appears that PFAS is a common component of landfills, and that it is found in this gas.

From the introduction:

Per- and polyfluoroalkyl substances (PFAS) are anthropogenic, ubiquitous chemicals of concern due to their persistence and potential human health effects. Some PFAS are found in consumer products, (1?6) often disposed in landfills at the end of their useful life. (7?9) Landfills are estimated to receive ?50% of all municipal solid waste generated in the U.S. (9)
While volatile (neutral) PFAS have been measured in the gas phase of air surrounding landfills, (10?13) their presence in the gas generated during the anaerobic biodegradation of waste buried in landfills (i.e., landfill gas (LFG)), (14?16) collected from within landfills (e.g., from a gas well or header pipe), has not been characterized, which is needed to estimate the mass released from landfills to the atmosphere. (17?19) Previous analysis of biogas collected from sewage sludge identified peaks corresponding to fluorinated compounds at less than the limit of quantitation (LOQ) and indicated the potential release of PFAS to the gas phase. (20) In contrast, the presence of nonvolatile (ionic) PFAS (e.g., perfluoroalkyl carboxylates and perfluoroalkyl sulfonates), in landfill leachate and in LFG condensates, is well documented. (7,17?19,21,22)
A methodology for sampling PFAS in LFG has not yet been described, but is challenging because LFG consists of 40%–60% (v/v) methane, (15,23?26) which is above the upper explosive limit of methane (17%). (27) For this reason, sampling equipment must be explosion proof. Given the likely higher concentrations of PFAS in LFG compared with ambient air, a technique for collecting lower volumes (less than 1 L) of LFG over shorter time periods is needed. Previously described passive and active sampling techniques for ambient air required collection of 100 to 1000 m3 over periods of hours to days. (10?13) Organics (non-PFAS) in biogas and LFG were previously analyzed using sorbents. (20,23) While thermal desorption (TD) was used for PFAS in ambient air (not associated with landfills), (28,29) indoor air, (30,31) and from aqueous film forming foam, (32) the TD-based approach has not been described for sampling PFAS in LFG given the complexity of LFG collection systems─composed of multiple sections─and the presence of several sampling locations at a given site. (15,23,24,26) Compared to other sampling strategies, TD is solvent free, suitable for collection of smaller volumes over shorter sampling periods, and interfaced directly with gas chromatography–mass spectrometry (GC-MS). Although a TD-based sampling methodology does not differentiate between gas- and particle-phase PFAS, data for neutral PFAS in ambient air near landfills determined that the particle–gas phase ratios for neutral PFAS ranged from 0.001 to 1, which indicates that neutral PFAS are predominantly in the gas phase, (12,13) further supported by past works. (33?35) In contrast, a ratio of 1–10 was reported for ionic PFAS of the same carbon length. (12,13)

A sampling system was constructed to collect LFG from both individual gas wells and the main pipe (header), which collects gas from an entire landfill, (26) for the analysis of neutral PFAS by TD-GC-MS. The method was optimized for up to 25 target neutral PFAS across eight different classes and to detect 14 suspect PFAS from four classes. The optimized method was demonstrated using LFG samples collected from landfills in the southeastern U.S. The methodology is a prerequisite for a larger study aimed at quantifying the emissions of neutral PFAS from ?30 landfills of various climates across the U.S...

Some graphics and some findings from the brief paper:

The caption:

Figure 1. Schematic diagram of the landfill gas sampling system.

The caption:

Figure 2. Concentrations of target neutral PFAS in LFG with volumes of (a) 200 and 400 mL and (b) 500 to 5000 mL (only single samples), collected at a sampling flow rate of 100 mL/min on different days, all at LF1 (Table S4).

A table of results:

On the bright side, as I noted elsewhere, PFAS are thermally degraded, at least partially, by heat. Thus burning the gas will lead to its decomposition, albeit generating some fluorophosgene, difluorocarbene, and trifluoroacetic acid.

I noted this mechanism recently in this space:

Some Aspects of the Thermal Degradation of Gaseous Perfluorinated (PFAS) Substances.

For the record, I favor the high temperature steam or dry (CO2 as the oxidant) reforming of municipal and some agricultural wastes using nuclear heat, particularly in a radiation field, mineralizing PFAS into barium or calcium fluoride and barium or calcium carbonate.

The journal in which this paper appears has a nice article on the subject of the degradation of short chained fluorinated acids, suggesting that the growing crisis with trifluoroacetic acid concentrations may also be addressed using radiation fields:

Transient Kinetics of Short-Chain Perfluoroalkyl Sulfonate with Radiolytic Reducing Species Zhiwen Jiang, Daniel Adjei, Sergey A. Denisov, Mehran Mostafavi, and Jun Ma Environmental Science & Technology Letters 2023 10 (1), 59-65

The paper, which I meant to cover here, but never found the time to do so, focuses on short chain perfluorosulfonates, but probably has implications for TFA, PFA, BFA...etc...

Steam or dry reforming of municipal waste would have the advantage of CO2 capture for use, as well as the destruction of persistent organic pollutants, of which PFAS are merely a subset.

This is feasible to my mind and it is a topic I attempt to discuss with my son as frequently as is possible, since he may be in a position some day, some time off, to actually realize this dream of mine, albeit after I'm dead.

Have a nice day tomorrow.

May 31, 2023

I just found out this weekend that our cat is 17 years old.

My sister-in-law asked if we could "watch" the cat at our house for a few weeks while she and her ex-husband sorted out living arrangements as they divorced. That was 10 years ago. The cat's still here.

My sister in law came this weekend to visit us for Memorial Day, and I asked about the cat, which she got for her daughter. It appears she got it when her daughter was four. Her daughter's now 19. We thought that the cat was a kitten when they adopted her from a shelter, but it turns out that the shelter said she was about 2.

It adds up, thus, to 17.

She's basically an indoor cat; she'll step outside to chew on grass, but never goes far from the front door of our house.

She looks like she's in pretty good shape although she is getting bony.

How long do indoor cats live?

I've only had outdoor cats and they all managed to get themselves killed at a young age.

I've gotten used to that cat.

May 31, 2023

Carbon Intensity of Electricity of Some European Grids With Nuclear Power 5/31/23 3h21m Paris Time

South Central Sweden: Carbon intensity 15 grams CO2/kWh.

Finland: Carbon Intensity, 46 grams CO2/kWh.

France: Carbon Intensity 21 grams CO2/kWh.

Electricity Map

May 30, 2023

Metals, the Carbon Impact of Metals, and So Called "Renewable Energy."

I will briefly refer to two papers, one from three years back that is already highly cited, and another in a very recent issue of the journal Environmental Science and Technology.

The two papers are:

Sonter, L.J., Dade, M.C., Watson, J.E.M. et al. Renewable energy production will exacerbate mining threats to biodiversity. Nat Commun 11, 4174 (2020).

...and...

Decomposition Analysis of the Carbon Footprint of Primary Metals Kajwan Rasul and Edgar G. Hertwich Environmental Science & Technology 2023 57 (19), 7391-7400.

The abstract for the first one, which is open sourced and can be read in its entirety, begins with a nonsense statement, this one:

Renewable energy production is necessary to halt climate change and reverse associated biodiversity losses.

The abstract clearly contradicts the text, since so called "renewable energy" drives rather than reverses biodiversity losses. The first clause that "renewable energy production is necessary to halt climate change" is not supported by any data. The trillions of dollars already squandered on solar and wind energy in this century has only resulted in the acceleration of the rate of climate change. Both have proved worthless, useless, without value, inconsequential, meaningless...a thesaurus is a wonderful thing...if the goal is to address climate change. That was never the goal of so called "renewable energy;" the goal was to attack the only possible effective tool to address climate change while protecting ecosystems, nuclear energy.

I came across the first of these references - there are literally hundreds, if not thousands, of papers focusing on the extreme and destructive material and land impacts of so called "renewable energy" when an antinuke began complaining about mining in connection with nuclear energy, although nuclear energy has the highest energy to mass ratio known, and thus is the least dependent form of energy on mining. Reality has a way of presenting itself; all efforts to obscure it by obfuscation are futile.

An antinuke complaining about mining is rather like Ron Desantis complaining about racism.

The paper is open sourced but some text is provided for convenience:

Climate change poses serious threats to biodiversity1,2. To keep temperature increases below 2?°C, and halt associated biodiversity losses, 140 nations committed to the Paris Climate Change Accord to reduce anthropogenic greenhouse gas emissions by 90% (from 2010 levels) and reach carbon neutrality by 21003. Energy sector innovation is where most progress is achievable4, but since renewable energies currently account for only 17% of global energy consumption5, significant production increases must occur to phase out fossil fuel use6. However, the production of renewable energies is also material-intensive—much more so than fossil fuels7—meaning that future production will also escalate demand for many metals8,9,10,11. It is unlikely that these new demands will be met by diverting use from other sectors or from recycling materials alone12,13. When required commodities exist in biodiverse countries that lack strong resource governance, such as the world’s second largest untouched lithium reserve in Bolivia’s Salar de Uyuni salt pan5—a biodiverse area currently untouched by mining14—mining poses serious threats to species and ecosystems15.

The Salyar de Uyuni salt pan is just one example of course of a region where lawlessness prevails in mining.

A word about that "percent talk," 17%, in this text. Combined, as of 2021, solar and wind produced 12 Exajoules of the 624 Exajoules of Energy consumed by humanity in that year, this after the expenditure of 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.) Solar and wind are thus responsible for less than 2% (in "percent talk" ) of the world energy supply. The bulk of rest of the 17% comes from strip mining forests (biomass), and the destruction of major river systems (hydro). Neither of these systems will be available for huge growth in increasingly destabilized weather. Indeed forests all around the world are burning before we can chop them up and send them up smokestacks while claiming they're "renewable." The cause is climate change.

Source for the 3.3319 trillion figure: Global Trends in Renewable Energy Investment 2020 (Figure 42, page 62).

The second paper notes that metal demand is rising at an enormous rate, even without trying to bulldoze vast stretches of land to make industrial parks for wind turbines that will be landfill in 20 years.

An excerpt:

Materials, and especially metals, play a key role in the development of modern economies. While population only increased fourfold from 1900 to 2010, (1) the rate of material extraction increased 11-fold. (2) This discrepancy is mainly driven by a fivefold increase in per capita stock of manufactured capital, such as buildings, infrastructure, and durable goods. (2) In the last couple of decades, production rates of all primary metals have increased significantly faster than global population (Figure 1). In the case of iron and steel, aluminum, and nonferrous metals, their rates have even grown substantially faster than the global gross domestic product (GDP). Especially aluminum stands out with a growth of 1.8 times the GDP growth. Gold is the only metal that has experienced stagnation for a prolonged period (more than 2 years) but has increased steadily in the last 10 years of this study.

Metal production has severe environmental impacts, both locally and globally. On a local scale, it is mainly a matter of waste and toxicity, while globally it has been recognized as a main contributor to climate change. (3) The latter is due to both high process emissions and energy use in metal production and its supply chain. Direct process emissions are for a range of metals identified as sources of emissions that are particularly difficult to abate, (4) while the high energy intensity of metal production uses roughly 8% of the total energy supply. (5)

Historically, greenhouse gas (GHG) emissions have been strongly coupled with increasing affluency through the increasing demand for goods. (6) Some international organizations, governments, and scenario models argue or assume that decoupling between increasing affluency and GHG emissions is possible through the concept of green growth. (7?12) On the other hand, some scientists have been critical of the possibility of a green growth pathway. (13?15) It is however uncertain if such decoupling in a green growth scenario is universally feasible, or if it is only the case for specific metals and their GHG emissions. (16) These emissions can be reduced through both technological developments and environmental policies. (12,17) Since the early 1990s, efforts have been made in mitigating GHG emissions through international agreements. (18,19) Studies have shown that emissions in the upstream supply chain of metals have increased significantly in the last two decades especially due to the rapid expansion of metal refining in China, which relies heavily on coal. (20?22) However, it is not clear how different technological and socioeconomic drivers have impacted these emissions and what role they have played in a potential decoupling.

The paper notes that the highest rates of metal consumption are in developing countries, and gives "unsurprising" reasons for this:

The decomposition results showed that it is mainly high-income regions, which have managed to reduce their emissions embodied in metal consumption. This is unsurprising for three reasons. First, these regions have the highest metal consumption rate per capita and thereby the largest potential for reduction. Second, they have also built most of their essential infrastructure in the recent century, whereas the other regions still require metals for such infrastructure to develop their economies and improve the well-being of their population. (63) Other IO studies have shown that the global carbon footprint of metals is increasing due to rising infrastructure in especially China, (20,36) where there is a strong reliance on coal in industry. (21) Third, the high-income regions are the main driving forces behind the climate deals of the recent decades. (18,19) These may bring changes in consumption patterns and services, which in turn may reduce metal consumption and the associated environmental impacts. (3,64?66) However, consumption patterns are often bound to culture and may take long to change profoundly. An example of such cultural tradition that heavily impacts metal consumption is that houses become valueless after one generation in Japan. (67) Hence, old houses are demolished, and new metal is needed to build a new house. This may be a reason for the relatively high metal consumption rate of JKTA when compared to Europe and the USA and Canada, where old houses are investments that usually increase in value.

One of the things notable about bourgeois types, for instance the battery worshippers who lack the moral strength to confront the issue of cobalt slavery, or wind energy advocates who couldn't care less about the conditions in the Baotou China lanthanide mines and refineries, is that they love to complain about developing nations from a lofty height of consumerism and self satisfaction.

If I hear one more complaint about how China alone is driving climate change while we're all innocent in the West, I'm going to throw up. The Chinese (nor the Indians) did not agree to remain impoverished so rich and oblivious Americans could sit in front of their computers and worship pictures of wind turbines.

Anyway, the argument that the word "renewable" in the term "renewable energy" is as dishonest as is the continued insistence in the face of rapidly accelerating rates of carbon dioxide accumulation in the planetary atmosphere can, or should be addressed by "renewable energy."

Reality does not respond to wishful thinking.

I trust you've enjoyed the long holiday weekend.

May 29, 2023

A New Mechanism by Which Air Pollution Kills: Does It Drive Obesity?

Here's a surprising paper I came across this afternoon: PPAR? As a Potential Target for Adipogenesis Induced by Fine Particulate Matter in 3T3-L1 Preadipocytes, Yaqiang Cao, Yuanyuan Chen, Ke Miao, Shuyi Zhang, Fuchang Deng, Mu Zhu, Chao Wang, Wen Gu, Yixuan Huang, Zijin Shao, Xiaoyan Dong, Yufeng Gong, Hui Peng, Hui Yang, Yi Wan, Xudong Jia, and Song Tang, Environmental Science & Technology 2023 57 (20), 7684-7697.

The language in the title may be somewhat abstruse; the PPAR (Peroxisome proliferator-activated receptor) class of proteins regulate metabolism. Classes of PPAR are involved in sugar metabolism and insulin sensitivity; they are drug targets for diabetes. PPAR? is particularly involved in the storage of fats and the generation and function a class of cells known technically as adipocytes, colloquially as "fat cells," grown in culture from 3T3-L1 precursors.

I often note, usually when confronted by antinukes carrying on insipidly about used nuclear fuel, which has a spectacular record of never actually killing anyone despite endless public fetishes that are toxic cultural universals, since antinukism kills people, that about 7 million people a year are killed by air pollution. Nuclear power, where not obstructed by toxic fetishes, prevents this environmental driver of mortality.

Often, sometimes with excerpts, I cite this paper from a prominent medical journal, to indicate the rate at which the antinuke mentality kills 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).

If one looks into the matter - the paper is open sourced - one can find indications that the mechanism by which air pollution kills people is, unsurprisingly, very much the same way that smoking cigarettes kills people, lung diseases, including cancers, heart diseases, and stroke.

The paper cited at the outset would suggest an alternate mechanism by which air pollution might kill people - not this is likely to inspire anyone now doing so from complete indifference while whining about nuclear fuels - by driving obesity. If true, this may suggest that the death toll from ignoring air pollution may be much larger than 7 million people per year, 19,000 people per day, 800 people per hour, more than Covid killed on its worst day.

I'm not going to spend a lot of time on this paper; it's largely technical, and while my day to day life is involved in this sort of thing, it may be too esoteric in this setting. However some text is illustrative and hopefully not all that technical.

From the introduction:

Obesity has been identified as a major risk factor for the comorbidity of many noncommunicable diseases, including cardiovascular diseases, stroke, diabetes, and metabolic syndrome, leading to enormous psychological, social, and economic burdens. (1,2) More than doubling over the past few decades, the prevalence of obesity has risen dramatically worldwide. (3) In 2015, 609 million adults were estimated to be obese, representing approximately 39% of the world’s population. (4) The usual explanations given for the current obesity pandemic are individual risk factors, such as genetic determinants, physical inactivity, and a calorie-dense diet. (5) However, mounting evidence from epidemiological observations and experimental research indicates that environmental drivers, such as endocrine-disrupting chemicals (EDCs), might be another primary contributor. (6) As a subset of EDCs, obesogens have gradually garnered wider academic and public attention owing to their abilities to strongly promote adipocyte differentiation in vitro and induce obesity in vivo by interfering with the normal development and control of adipogenesis and energy homeostasis. (7)

Currently, over 90% of the global population lives in areas where ambient levels of fine particulate matter (PM2.5) exceed the World Health Organization (WHO) annual air quality guideline of 5 ?g/m3. (8) Exposure to PM2.5 has been significantly and positively associated with the increasing incidence of obesity and relevant metabolic diseases. (9) Animal studies have also demonstrated that exposure to PM2.5 increased visceral adipogenesis in rodents. (10) As a suspected obesogen, PM2.5 is a highly complex mixture that is typically composed of a wide array of chemicals [e.g., heavy metals, water-soluble inorganic ions, organic carbon, elemental carbon, and polycyclic aromatic hydrocarbons (PAHs)]. (11,12) With a relatively large surface area, PM2.5 can enrich many exogenous environmental pollutants, some of which readily accumulate in lipid-rich tissues (e.g., adipose tissue). Indeed, multiple classes of well-defined obesogens [e.g., di-n-butyl phthalate (DBP) and bisphenol A (BPA)] have been frequently identified within PM2.5, although their detection rates and concentrations vary by sampling regions and times. (13) Therefore, studies on the adipogenic properties of PM2.5 on adipose tissue differentiation, metabolism, and function are urgently needed to clarify the pathogenesis of PM2.5 in promoting obesity and metabolic complications.

The 3T3-L1 mouse preadipocyte cell line has been recognized as a well-established in vitro model for assessing the modulation of adipogenesis by obesogens. (14) Adipocyte differentiation is strictly regulated by a transcription network, such that the orderly expression of certain genes, such as peroxisome proliferator-activated receptor ? (PPAR? ) and fatty acid binding protein 4 (Fabp4), are the primary regulators that promote the maturation and development of adipocytes, as well as influencing lipid metabolism, inflammation, and glucose homeostasis. (15) Many in vitro studies have shown that obesogens can disrupt the differentiation and enhance the lipid accumulation of 3T3-L1 preadipocytes by directly binding to PPAR? or activating the PPAR?-mediated pathway. (16) Recently, high-throughput omics approaches (e.g., transcriptomics and metabolomics) have shown promise in comprehensively elucidating global changes at different biomolecular levels to better understand the complex modes of action (MOA) underlying the adipogenesis induced by obesogens. (17) Specifically, lipidomics, a branch of metabolomics, has provided promising and unbiased lipid profiling for the investigation of biomarkers and the pathogenesis of dyslipidemia and obesity. (18) Understanding the toxicities and MOA of PM2.5 on pre- and mature adipocytes will be enhanced by systems biology approaches.

By using the 3T3-L1 preadipocyte differentiation model, we aimed to comprehensively evaluate the obesogenic effect of PM2.5 exposure on adipogenesis and explore its biomolecular mechanisms through the integration of cellular assays and global transcriptomic and lipidomic approaches. To further clarify the pivotal role of PPAR?-mediated effects in PM2.5-induced adipogenesis, the PPAR? antagonist T0070907 was utilized for an intervention experiment conducted concurrently with PM2.5 exposure...

Indeed in these mouse cell experiments the authors found evidence that air pollution may indeed be a driver of obesity.

The study details can be found at the original paper; a subscription is required.

The conclusion suggests that PM2.5 may well drive the "obesity pandemic:"

Overall, this study is the first to demonstrate that PM2.5 significantly promoted the intracellular lipid accumulation and adipogenic differentiation of 3T3-L1 preadipocytes. Global transcription and lipid profiling revealed that these in vitro changes were at least partly mediated by activating the PPAR? signaling pathway, upregulating critical markers within the adipogenic transcriptional cascade, and remodeling lipid metabolism, possibly leading to adipose tissue malfunctions and excessive fat storage in the body. Targeting PPAR? with T0070907 significantly inhibited the observed changes at the cellular and biomolecular levels, suggesting that PPAR? could be used as a potential therapeutic target in the treatment of PM2.5-induced adipogenesis. The current findings thus provide a possible biomolecular mechanism for the etiology of PM2.5-induced obesity and some experimental basis for addressing the obesity pandemic...

The authors note the limitations of their study, one being that the chemical nature of PM2.5 varies with geography; it's all toxic, but the toxicity may have differing mechanisms.

I often amuse myself by asking antinukes to show that the 70 year history of the storage of commercial used nuclear fuel - which I personally regard as a valuable resource as opposed to a "waste" - has resulted in the deaths of as many people as will die in the next six hours from air pollution, more than 4500 people. None of this is ever likely to make them think about the consequences of their petty obsessions and frankly, insane, paranoia, but when asked they never get back with a serious answer, because the 70 year history of the storage of used nuclear fuel has not killed as many people as will die from air pollution will kill in the next six hours.

Perhaps the number I use, 4500 deaths every six hours, is, however, too low.

It will be interesting to follow this line of thought.

I'm not sure I can blame antinukes for the fact that I am fat, but I do blame them for their pronounced indifference to human life, as well as their indifference to climate change, driven by dangerous fossil fuel waste (with PM2.5 being just one component), the latter, climate change, over the long term, to be far more serious than the former, the vast death toll associated with air pollution.

I hope you had a pleasant holiday weekend.

May 28, 2023

Sir Geoffrey Ingram Taylor's Earth Shattering Discovery of the Taylor Cone Took Place at Ages 78-83.

Recently, as I noted yesterday in a post in this space, I've been reading about coupled ion mobility spectroscopy and mass spectrometry.

The paper I'm reading has a fascinating discussion of the history of these techniques, and finally, after all these years of seeing the words "Taylor Cone" thrown about without really thinking of what they mean, I decided to look the matter up.

The existence of the "Taylor Cone" is a critical concept in the development of electrospray ionization, for which John Fenn won the Nobel Prize, a technique that, because of its importance in mass spectrometry, has huge, indispensable application in environmental science, drug discovery and development, physiology, materials science, synthetic chemistry, biochemistry, physics, etc., etc.

I ended up at the Wikipedia page of Sir Geoffrey Ingram Taylor. He was, in fact, a remarkable scientist, a major player in optics, fluid dynamics (including aerodynamics, especially in World War I, were he worked on propeller strength and the development of the parachute, the Manhattan Project as a British representative, particularly on implosion technology, and between the ages of 78 and 83.

Between the ages of 78 and 83, Taylor wrote six papers on electrohydrodynamics. In this work he returned to his interest in electrical activity in thunderstorms, as jets of conducting liquid motivated by electrical fields. The cone from which such jets are observed is called the Taylor cone, after him.

I was unaware of this great man.

So much for being "too old." I have noted, with deep respect, that our "too old" President is one of the greatest Presidents we have seen.

May 28, 2023

At the G7 in Hiroshima, the US, Japan, South Korea Announce Support for Romanian Reactor Development

$275 Million for NuScale VOYGR deployment in Romania announced

Caption:

President Biden met with the leaders of Canada, France, Germany, Italy, Japan, and the United Kingdom at the G7 Summit, held May 19–21 in Hiroshima, Japan. (Also pictured are representatives of the European Commission and European Council.)

Some text:

On the sidelines of the G7 summit in Hiroshima, Japan, over the weekend, the Biden administration and partners Japan, South Korea, and the United Arab Emirates announced a public-private commitment of up to $275 million to support the advancement of NuScale Power’s small modular reactor project in Romania.

The announcement was part of a commitment made by world leaders last year at the G7 summit at Schloss Elmau in Germany to mobilize $600 billion in infrastructure investments under a new program—the Partnership for Global Infrastructure and Investment.

Funding for the NuScale project will support procurement of long lead materials, phase two of front-end engineering and design (FEED) work, provision of project management expertise, site characterization and regulatory analyses, and the development of site-specific schedule and budget estimates for project execution, according to a May 22 NuScale press release. In addition, the U.S Export-Import Bank (EXIM) and U.S. International Development Finance Corporation (DFC) issued letters of interest for potential support of up to $3 billion and $1 billion, respectively, for project deployment, the Portland, Ore.-based SMR developer said.

In addition to EXIM and DFC, partners committed to advancing the SMR project include the Japan Bank for International Cooperation; DS Private Equity (South Korea); EXIM Bank Romania, Nuclearelectrica, and Nova Power & Gas (Romania); and Emirates Nuclear Energy Corporation (UAE). According to a State Department release, ENEC’s involvement in the Romanian project, through in-kind contribution of nuclear experts, represents the first nuclear energy–focused activity undertaken within the U.S.-UAE Partnership for Accelerating Clean Energy (PACE) platform. PACE was launched in November 2022 to catalyze $100 billion in financing, investment, and other support to deploy 100 new gigawatts of clean energy capacity by 2035.

CEO excitement: “Support from the Biden administration and international partners is a signal to energy markets around the world that NuScale SMRs are an important new technology solution to global decarbonization and that Romania has the capabilities and experience to support its deployment,” said John Hopkins, NuScale’s president and chief executive officer. “We are thrilled public-private partnerships are helping deploy our leading SMR technology as soon as 2029.”

May 27, 2023

Photon lights a path towards a nuclear clock

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

Subtitle:

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.

May 27, 2023

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.

May 27, 2023

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.

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