NNadir

NNadir's Journal

September 10, 2020

The Chemistry of the Class of Poisons Putin Utilized to Poison Navalny: Novichok A234.

The paper I'll discuss in this post is this one: Novichoks – The A group of organophosphorus chemical warfare agents (Marcin Kloske Zygfryd Witkiewicz, Chemosphere Volume 221, April 2019, Pages 672-682).

I came across this paper as a result of a news item in Science: How German military scientists likely identified the nerve agent used to attack Alexei Navalny (Richard Stone, Science September 8, 2020.)

An excerpt:

On 2 September, German Chancellor Angela Merkel revealed that Alexei Navalny, a Russian opposition politician, had been poisoned with a nerve agent “identified unequivocally in tests” as a Novichok—one of a family of exotic Soviet-era chemical weapons. Merkel, a chemist by training, did not reveal the nature of the tests, conducted in a military lab in Munich. But scientists familiar with Novichoks have a good idea how the toxicological sleuths went about it—and are impressed by how fast the culprit was unmasked.

Navalny fell ill on 20 August after drinking a cup of tea at a Siberian airport. He lapsed into a coma and was flown to Berlin 2 days later; in a statement yesterday, the hospital treating him said he is out of the coma and “responding to verbal stimuli.” Navalny’s supporters have accused Russian operatives of slipping poison into the tea—a charge that seems credible in light of Russia’s recent record of using toxic substances to silence critics.

Novichok A234 was the weapon of choice for settling a score with a former Russian spy, Sergei Skripal, in Salisbury in the United Kingdom in March 2018. In a botched operation, two Russian intelligence officers left a trail of evidence in the attempted assassination of Skripal, whose daughter Yulia also fell ill after exposure to A234. They survived, but a woman who later came across a perfume bottle containing the substance died.

The Salisbury scandal brought Novichoks out of the shadows. After a Russian chemist in 1992 divulged some details about the exquisitely toxic nerve agents—there are at least seven of them—the U.S. government and allies clamped down on open discussion; Novichoks were classified as secret. A234’s brazen use in the United Kingdom led to a public reckoning...

Personally, I don't think that the uncovering of Novichoks in Nalvany was particularly challenging. It is really an issue of seeing the symptoms, knowing some history, and utilizing some bioanalytical high resolution mass spectroscopy to confirm the suspicions.

I have no idea whether Vladmir Putin, who owns our "President" outright - has read a translation of Edgar Allan Poe's The Cask of Amontillado but in choosing his poisons, Polonium-210 in the case of Alexander Litvinenko, Novichok A234 in the case of Sergei Skripal, and now, for Navalny Novichok again, by using poisons to which he, and he alone, has unique access, so there can be no ambiguity about who is doing the killing, he seems to take Poe's remarks on revenge in the story seriously:

I must not only punish but punish with impunity. A wrong is unredressed when retribution overtakes its redresser. It is equally unredressed when the avenger fails to make himself felt as such to him who has done the wrong. It must be understood that neither by word nor deed had I given Fortunato cause to doubt my good will. I continued, as was my in to smile in his face, and he did not perceive that my to smile now was atthe thought of his immolation.

.

The full Chemosphere paper is a rather interesting review of the chemistry and history of these chemical warfare agents that are uniquely Soviet/Russian, although they got their start in Germany.

An excerpt from the text:

Organophosphorus-based chemical warfare agents (OP CWAs) are the most toxic substances amongst synthetic chemical ones. Notwithstanding the foregoing, as well as the Chemical Weapons Convention (CWC) spirit of the law (Witkiewicz et al., 1996), still exists the threat of the use of chemical warfare is almost growing day by day (Crowley et al., 2018; Guidotti and Trifirò, 2016; Kenyon et al., 2005; Mangerich and Esser, 2014; Robinson, 2008, 1998; Rogers, 2014; Simonen, 2017; Stock, 1998; Üzümcü, 2014). CWAs may be used, not only on the battlefields, during military operations, but still is growing the possibility of its terrorist's use. CWAs could be the tool for political opponents' killings. The threat is still to be expected (Croddy et al., 2011; Tucker, 2007). In March 2018 an attempt was made to murder Sergei Skripal with a new poisonous agent called Novichok. In fact, it is a group of chemical compounds with very high toxicity. The information about these substances is incomplete, often contradictory. Therefore, this paper describes the available information about this group of chemical compounds belonging to OP CWAs.

Up to the moment, in literature there is a division of OP CWA(s) into G and V (sub)groups. These groups are well descripted in the sets of articles and books, as well as are quite well described in the undisclosed military literature. In this paper we describe G and V group in general terms, with strict Novichok characterization as one of OP CWA, capable to inhibit acetylcholinesterase (AChE). Novichoks are described as A-subgroup, without clearly stating that they are organophosphorus substances with physicochemical and toxic properties similar to substances belonging to groups G and V. This is probably, due to the fact that there is no P-C binding in its molecules. However, these substances are organophosphorus compounds because its molecules contain phosphor and carbon atoms. Therefore, we believe that it is necessary to introduce the novel OP CWAs division into three subgroups: G, V and A. In this article we present a justification for this opinion.

Some history:

The chemical warfare history is probably as old as the humankind. Already in 400 BCE, during the Peloponnese War, the Sparta army used sulphur vapours against the Athens army. Later, chemical substances were used many times and in various forms during military operations. The highest victim number was caused by the chemical warfare use during World War I, between 1914 and 1918. As a result of the poisonous substances use on both sides of the conflict, 85.000 soldiers died, more than 1.2 million were permanently blinded, burnt and mentally mutilated (Delfino et al., 2009; Mangerich and Esser, 2014; Ramirez and Bacon, 2004; Sheffy, 2005; Shiver, 1929; Szinicz, 2005)...

...Nerve agents poisoning symptoms are associated with the autonomic nervous system stimulation by acetylcholine accumulation, which is not decomposed by acetylcholinesterase. The cholinesterase inhibition is the reason for this.
In addition to their immediate effects, nerve agents also have delayed effects. They take the form of psychological, neurological and cancer effects. There is also susceptibility to infectious diseases, liver disorders, pathological changes in blood and bone marrow as well as eye damage.

Nerve agents have been discovered in Germany before World War II during the development of organophosphorus pesticides. On an industrial scale, they started to be produced during the War...

...In 1936, the OP CWAs, compounds with code names G (G-group) has been discovered in Germany. On December 23rd this year, during his work on insecticides, Gerhard Schrader discovered the first chemical compound belonging to the G group. It is nowadays known as tabun. After a drop of tabun spilled on the laboratory table, Schrader and his assistant had myosis, dizziness and shortness of breath. It took them three weeks to recover. The Wehrmacht had been interested in the discovery and further hidden research was carried out in a military laboratory. The tabun was initially coded Le 100 and later Trilon 83. In 1938 in the Schrader's team was discovered compound with code-name T-144 and Trilon-46, known as sarin. This name is derived from the names of the first developers: Schrader, Ambros, Ritter and Linde. Sarin has been shown to be about 10 times more toxic than tabun.
Through research on tabun and sarin at the Heidelberg Institute, Kuhn and Henkel received a soman whose name is derived from the Greek word 'to sleep' or the Latin 'mace'...

... The tabun test production has been started before the World War II beginning. The test production process and equipment used in it were complicated. The industrial scale production during WW II was located in Dyhrenfurth, currently Rokita Chemical Plant in Brzeg Dolny (Poland). Approximately 3000 employees were engaged at the plant. Of these, several hundred were injured and at least several dozen died. About 10,000 to 30,000 tons of tabun were produced before the plant was taken over by the Soviet army and was probably moved to Dzerzhinsk, Russia. The slave labour force was employed to take part in tabun production. One of the inmates was prisoner of the concentration camp at the Dyhrenfurth plant, professor Andrzej Waksmundzki; in the next years outstanding chemist, analyst and chromatographer...

"Milestones" in the development of chemical warfare agents, table 3 from the text:

Structures of some known nerve agents, including Sarin, which was used for a terrorist attack in Japan in 1995, and again in Syria, by Putin's client, in 2018:

The caption:

Fig. 1. OP CWAs structural formulas for G-group nerve agents: tabun, sarin, soman, ethyl sarin, chlorosarin, cyclosarin, and DFP.

Some more text:

Novichoks has been discovered in the former Soviet Union as the development work on the third and fourth generation of chemical warfare agents (Averre, 1995; Kloske, 2018; Mirzayanov, 2009). These works included inter alia, the construction of binary munitions and delivery systems. The main research centre for CW was the State Institute for Scientific Research on Organic Chemistry and Experimental Technologies. Initially, only reconstructive research was being conducted on the works carried out in western laboratories. At the beginning of the 1970s, the highest authorities imposed on scientists the development of poisonous fourth generation substances on their own. These substances had to be:

a)
undetectable using standard chemical detection instruments fitted to the NATO member states armies in the 1970s and 1980s;
b)
able to penetrate the enemy soldier's body despite the application of individual protection measures;
c)
safer than previous generations of CWA during storage and combat use preparation;
d)
not mentioned in the lists (also precursors) of Chemical Weapon Convention.

As a result of these assignments, phosphonates and phosphates containing amidine and guanidine fragments in the molecule - Fig. 5 and formaldehyde oxime - Fig. 6, were invented. It is also worth mentioning that in the late 20th century, the German company Bayer developed an organophosphorus pesticide derivative, called Phoxim, whose use in agriculture was banned in 2007 due to its strong toxic properties - Fig. 7.

Figures 5, 6, and 7:

The caption:

Fig. 5. General OP CWAs chemical structures for amidine & guanidine X = F or S-alkyl; R1 = O-alkyl (phosphate derivative) or alkyl (phosphonate derivative); R2, R3, R4, R5 = H, alkyl, phenyl, -CN.

The caption:

Fig. 6. General organophosphorus derivatives of formaldehyde oxime formula; X1 = F; X2 = any halogen, CF2NO2, CN; X3 = any halogen, CN, R = O-alkyl (phosphate derivative) or alkyl (phosphonate derivative).

The caption:

Fig. 7. Phoxim structural formula

The programme under which Novichoks were developed was codenamed FOLIANT. The first public article on Novichok appeared in the weekly Moskovskie Novosti in 1992, on the eve of Russia ratifying the Chemical Weapons Convention. The authors were two chemists - Lew Fiodorov and Vil Mirzayanov. According to the authors, the Russian military-chemical complex was using funds received from the West for the implementation of disarmament agreements to build a modernised potential for conducting a chemical war. The authors revealed information allegedly in connection with their concern for the environment. They were working on measuring the concentration levels of harmful substances in facilities and outside facilities associated with the chemical weapon programme. These measurements were to prove whether foreign intelligence agencies could detect traces of BST production. The results of the measurements showed that the levels of toxic agents in the environment were about eighty times higher than the maximum safe concentrations. For unknown reasons only one article author - Mirzayanov was arrested and accused of state secrets treason

And so on...

Nice guy, the guy who owns your "President..."

Interesting paper, I think, scary but interesting.

I am not, for the record, in favor of banning chemistry, but like any technology, chemistry has a huge potential for abuse.

Have a nice, and where possible, safe, day.

September 10, 2020

Another Great Day For Renewable Energy in California.

This data comes from the CAISO website, Accessed 19:30 PST 09/09/20:

Big "Percents" today around noon, despite all the smoke:

Fabulous work "by 2020." They certainly addressed climate change by 2020:

Weekly average CO2 at Mauna Loa

Week beginning on August 30, 2020: 411.59 ppm
Weekly value from 1 year ago: 408.82 ppm
Weekly value from 10 years ago: 387.59 ppm
Last updated: September 9, 2020

Thank goodness they'll be closing their last nuclear plant "by 2024."

One never knows what could have happened at that nuclear plant, which has "only" been producing 2,246 MW of electricity all day long, constantly, in a single building. That sucks.

Heckuva job! Heckuva job!

So green, or, um, brown, or well, it's "by 2020," in any case.

We're doing great!!!

September 10, 2020

...what does that hand desire...

September 9, 2020

Editorial: Circularity. What's the Problem?

This editorial perfectly summarizes my personal outlook on environmental issues, so much so that I wish I had written it.

It's in the current issue of ACS Sustainable Chemistry and Engineering. Regrettably, I think it's behind a paywall:

Circularity. What’s the Problem? (Paul T. Anastas, ACS Sustainable Chem. Eng. 2020, 8, 35, 13111)

Some brief excerpts:

Every reader of this journal wishes to solve societal and ecological problems. Otherwise, they would be content with choosing to study scientific challenges that see no shame in irrelevance...

...Some of these historically derived yet lingering problems are receiving a tremendous amount of focus today. These include the following:

Achieving durability in materials without consideration for persistence in our bodies and the biosphere, especially our oceans.

Achieving convenience of data and information access while our electronics are dispersing critical metal and metalloid elements.

Achieving unprecedented crop yields while contaminating water resources with agricultural chemical runoff...

...The most recent example that must be examined is the very hot topic of the circular economy whose conceptual construct of moving toward cycling our material economy and eliminating waste is undeniably compelling. So what must be done in order to ensure this elegant theory is put into equally elegant practice? Perhaps a noncomprehensive list may include the following:

Ensure that energy, which is so often left out of the discussions of materials circularity, is integrated as the essential component that it is.

Ensure that the nature and character of the materials and energy within these cycles are considered at least as important as the stock, flows, and quantities of them.

Ensure that the timeframes and widely differing commercial lifespans of various materials streams are considered while attempting to build these circular constructs.

Ensure that the actual act of separation/isolation/purification of complex material streams—that can have in many cases, in itself, negative environmental, economic, and societal impacts—does not dwarf the original problem attempting to be solved.

Ensure that a circular economy construct definitionally envisions continuity and predictability of specified material flows that recognizes we are living in a dynamic world that will not become static in order to service circularity...

...The circular economy is an elegant concept that can contribute to a more sustainable society if its problem statement is thoughtfully designed and implemented wisely, with forethought for unintended consequences such as those outlined above. Alternatively, a half-designed circular economy would be yet another example of good intentions gone awry...

The part I have put in bold, is the most important of all the many insightful statements this editorial contains.

Without highly dense energy, utilized to maximal efficiency to assure equitable distribution, all is lost.

The issues in this editorial summarize perfectly what we must do to build a sustainable society, and delineate how far, exactly, we are from it.

September 7, 2020

Suspended Particle−Water Interactions Increase Dissolved 137Cs Activities in Typhoons (Fukushima).

The paper I'll discuss in this post is this one: Suspended Particle–Water Interactions Increase Dissolved 137Cs Activities in the Nearshore Seawater during Typhoon Hagibis (Hyoe Takata,* Tatsuo Aono, Michio Aoyama, Mutsuo Inoue, Hideki Kaeriyama, Shotaro Suzuki, Tadahiko Tsuruta, Toshihiro Wada, and Yoshifumi Wakiyama, Environ. Sci. Technol. 2020, 54, 17, 10678–10687)

The 137Cs isotope being discussed here is that released by the much discussed nuclear meltdowns at the Fukushima Dai-ichi nuclear power plant. It discusses the behavior of radioactive cesium released by the reactors when their containment buildings were damaged by a hydrogen explosion. The hydrogen was generated by a steam/zirconium interaction: Zr(s) + 2H2O(g) <-> 2H2(g) + ZrO2 solid. This reaction takes place at very high temperatures, temperatures that were experienced in the reactor core - zirconium is a key element in the structure of reactor cores as well as in the cladding of fuel elements - when the back up diesel generators that were supposed to keep the reactor cool during shut down failed when inundated with seawater.

Seawater killed about 20,000 people, but this is far less interesting to most people than the escape of radioactivity from the reactor, just as the 19,000 people who will die today, and died every day since March of 2011, and will die for an indefinitely defined people, from air pollution is not as interesting as the escape of radioactive materials from the reactors.

Cesium is a cogener of two elements that are essential to all living things, sodium and potassium. Physiologically cesium tends to behave very much like potassium, as does it's lighter cogener, rubidium. (Lithium is also a cogener of these elements.) Salts of these elements are all highly soluble in water, but cesium, and to a lesser extent, rubidium, tend to adhere to the surfaces of minerals commonly found in soil. The adsorption of cesium on to soil particles is a key point in the paper under discussion.

Natural cesium is not radioactive; natural rubidium and potassium are (slightly) radioactive owing to the naturally occurring long lived isotopes Rb-87 and K-40.

All human beings, indeed all living things, contain significant radioactivity as a result of the presence of potassium as well as its cogener rubidium, albeit to a lesser extent.

A common unit among many to quantify radioactivity is the "Bequerel," named for the scientist who discovered radioactivity in 1897. The Bequerel (Beq) is defined as one radioactive decay per second in any radioactive substance. The mBeq, the milliBequerel, which appears prominently in the paper is strictly speaking, 1/1000th of this amount. I mBeq is the number of decays that will take place in 1000 seconds. It is useful to think of mBeq as its reciprocal for values of less than 1000 mBeq; the reciprocal is the number of seconds (on average) that will pass before a decay is observed.

It can be shown that a 70 kg human being, owing to the natural radioactivity associated with potassium, will have about 4250 Beq of radioactivity in their flesh. There will also be some radioactivity associated with rubidium, which is not essential to human beings or other life forms but which is nonetheless almost always found in human and other living flesh. Rubidium can and does behave like potassium to some extent, particularly in instances of hypokalemia, too little potassium, where it can serve to ameliorate the shortage. One sometimes hears from a certain class of people that "there is no safe amount of radioactivity." These people are - there's no polite way to put this - idiots. Potassium is an essential element. Without potassium, one dies. It is thus essential that a healthy 70 kg human being contain around 4250 Beq of radioactivity.

In October of 2019, the Fukushima region was struck by a typhoon, and this paper is about the behavior of cesium which had adhered to soil particles after release from the reactor in this typhoon, as well as in high flow events in the rivers near the reactor.

From the introduction:

More than half of the radiocesium (i.e., 134Cs and 137Cs) released as a result of the Fukushima Dai-ichi nuclear power plant (FDNPP) accident was deposited and/or released into the nearshore ocean.(1?4) That radiocesium, however, moved via dilution and advection into the open ocean because the FDNPP is located at a coastal site, and the adjacent coastal waters are directly connected to the North Pacific Ocean. The decrease in radiocesium activity in water column in the offshore area to 0.1 Bq/L within 1 year(5,6) led to a rapid decline in Cs levels in marine organisms.(7?9)
In 2019, 8 years after the accident, 137Cs activities in the waters >30 km offshore from Miyagi to Chiba prefectures on the Pacific Ocean side of Japan were approaching the 2010 pre-accident levels (<2.4 mBq/L), and 134Cs, which has a half-life of 2.06 years, is now almost undetectable because four half-lives have passed.(10)

In contrast, 137Cs activities in nearshore waters in the vicinity of the FDNPP and within 10 km of Fukushima and neighboring prefectures(11) are still higher than those before the accident.(12) It is known that longshore currents flow primarily from the north of the Pacific Ocean side of Japan,(13) so 137Cs activities in nearshore waters were statistically higher in the south than to the north of the FDNPP from 2014 to 2016.(14) Furthermore, the quantification of the fluxes of 137Cs associated with direct release from the plant, re-entry of 137Cs from sediments through the submarine groundwater discharge (SGD), and fluvial inputs have indicated that direct discharge is the principal source of 137Cs that has maintained the relatively high 137Cs activities in the coastal waters during the 2 year period of 2014–2016.(6,14?16) However, the contribution of the ongoing release has declined. A sharp decline in radionuclide releases with water from the FDNPP after completion of a frozen soil wall in 2015 and of the water treatment system (e.g., pumping up the polluted water)(17) was probably the result of a reduction in the flow from the FDNPP because the flux from the plant has been decreasing since then.(15) Hence, it is likely that the constant flux of 137Cs from rivers, the catchment areas of which are contaminated, now plays a more important role in the activities of 137Cs in coastal areas in addition to the re-entry of 137Cs from sediments through SGD, which increases dissolved 137Cs in coastal waters of the wide area from both north and south of the FDNPP.(16)...

...It has been recognized that dissolved Cs+ is the dominant form of cesium in the ocean, but cesium is found in both particulate and dissolved forms in coastal areas.(21) Although riverine radiocesium includes both dissolved and particulate forms, a high proportion of radiocesium in rivers is associated with particles.(22,23) In particular, the heavy rainfall from typhoons, which cause devastating floods over wide areas, could result in contaminated surface soils being swept into rivers. In fact, the particulate fraction of radiocesium accounted for almost 100% of the radiocesium in the particulate phase after the typhoon of September 2011, and the fluxes of particulate radiocesium accounted for 30%–50% of the annual radiocesium flux from inland to coastal ocean regions in 2011.(22) In addition to elucidating the dynamics of dissolved radiocesium in the marine environment, it is necessary to understand the dynamics of its particulate phase and the interactions between dissolved and particulate radiocesium when river water mixes with seawater in the coastal areas, in which salinity changes markedly from 0 to 34.

There are several studies available in the literature concerning the behavior of radiocesium in river–sea systems: Although much of the radiocesium carried by rivers is in particulate form (i.e., adsorbed onto suspended particles), the salinity increase along the system results in the desorption of this radiocesium from the riverine suspended particles, thus increasing radiocesium activity in the dissolved phase in coastal seawaters (Figure 1).(24?32)...

... The goal of this study was therefore to explore the distribution of radiocesium in dissolved and particulate phases in the downstream reaches of rivers and the nearshore and offshore waters south of the FDNPP shown in Figure 2 with their catchment areas and mean 137Cs inventories in Table 1 (see detailed information on sampling sites and methods in the Supporting Information). Particularly, we focus on to what extent the desorbed fraction of riverine radiocesium contributed to the elevated levels of 137Cs in the dissolved phase in the nearshore areas after the heavy rainfall from typhoon Hagibis in the middle of October 2019...

Figure 1:

The caption:

Figure 1. Schematic diagram of riverine suspended particle behavior (light brown arrows) along the southward-flowing coastal current (blue arrow) including high radiocesium water from the plant in the coastal zone of Fukushima Prefecture from the FDNPP to the south of the prefecture. The dark blue arrow indicates the ground water discharge. The box at the right hand indicates sources of (1) the FDNPP site local sources (that can come in many forms, from GW at the site to tank leaks to over land contamination/rain inputs, etc.), (2) the more disperse release from GW associated with beach sands (Sanial et al.(16)), and (3) rivers and desorption. Riverine suspended particles introduced into the marine environment provide dissolved radiocesium through the desorption process while drifting in the longshore current.

The caption:

Figure 2. Sampling stations in the vicinity of the FDNPP (red circles: stations in downstream reaches of rivers; light blue circles: nearshore stations; dark blue circles: offshore stations). Area ? is the area within a 30 km radius of the FDNPP. Area ? is the area outside of Area ?. The spatial distribution of 137Cs inventory is based on the third airborne survey by the Ministry of Education, Culture, Sports, Science and Technology (MEXT) in 2011; the 137Cs inventory data were obtained from the website of the Japan Atomic Energy Agency; Airborne Monitoring in the Distribution Survey of Radioactive Substances (https://emdb.jaea.go.jp/emdb/portals/b1010301/).

Table 1:

The following figure refers to large volumes of water passed through a weighed dried 0.45 micron filter, designed to collect suspended particles, drying and weighing and then performing the counts of radiation obtained. The details can be found in the supplemental information which is open and free at the web page of the full paper.

The caption:

Figure 3. Distribution of (A) temperature (Temp.), (B) salinity (Sal.), (C) suspended particles, and (D) particulate 137Cs in rivers (Tomioka, Kido, Asami, Natsui, Fujiwara, Same, and Binda rivers) and adjacent nearshore (S1–S6) and offshore (O1–O12) stations. Gray circles indicate the geomean value in each station. Errors are not shown in this figure for readability but are listed in Table S1.

From the following graphic, one can estimate how much river water one would need to drink to get a single Beq of cesium-137.

The caption:

Figure 4. Distribution of (A) dissolved 137Cs, (B) particulate 137Cs, (C) percentage of particulate 137Cs in total 137Cs, and (D) Kd values in rivers (Tomioka, Kido, Asami, Natsui, Fujiwara, Same, and Binda rivers) and adjacent nearshore (S1–S6) and offshore (O1–O12) stations. Gray circles indicate the geomean value in each station. Errors are not shown in this figure for readability but are listed in Table S1.

Radioactivity as a function of distance to the shoreline.

The caption:

Figure 5. Variation in the river–nearshore–offshore system as a function of distance from the shoreline (0 km) in (A) 137Cs in particles, (B) dissolved 137Cs, (C) particulate 137Cs, and (D) Kd values. Negative distances indicate the fluvial area; positive distances indicate the offshore area. Errors are not shown in this figure for readability but are listed in Table S1.

The caption:

Figure 6. Light blue and blue bars indicate the estimated desorbed 137Cs activity (DesCsdis in eq 2) and observed dissolved 137Cs activity in which estimated desorbed activity has been deducted. Blue bars could originally include seawater through ongoing release from the FDNPP facility and re-entry through SGD. (A, B, C) Fraction (f) in eq 2 = 0.03 and (D, E, F) f = 0.3. Graphs on the left side of each figure are the pre-typhoon period in 2019 (high-river-flow condition from June to September). Graphs on the right are from the post-typhoon period. Dissolved 137Cs activity for offshore in (A) and (D) is mean value of station O1–4 (6.6 mBq/L). Dissolved 137Cs activity for offshore in (B), (C), (E) and (F) is mean value of station O5–12 (3.2 mBq/L). An asterisk (*) indicates a 137Cs concentration of 12 mBq/L at station TD-9 (37°20.0?N,141° 4.3?E) sampled on 14 Nov. 2019. Double asterisks (**) indicate a 137Cs concentration of 11 mBq/L at station M-G0 (37°5.0?N,141°8.4?E) sampled on 2 Nov. 2019. Both of these values were provided by the Nuclear Regulation Authority (https://radioactivity.nsr.go.jp/en/list/292/list-1.html).

The overall amount of cesium-137 released into the ocean is rather prodigious, on the order of GBq/day. A unit of radioactivity the Curie (Ci) is roughly equal to the number of decays in one gram of radium, = 3.7 X 10^(10) Beq, 37 megaBeq. Thus amounts approximating a Curie/day leach into the ocean.

However, the ocean contains vast amounts of potassium. I have done some calculations elsewhere to show how much radioactivity is present in the ocean from potassium alone: How Radioactive Is the Ocean?. In this calculation, I showed that the potassium associated radioactivity of the ocean was approximately 530 billion curies, or 2 X 10^(22) Beq, 20 zetaBeq.

I trust you've having a pleasant Labor Day afternoon.

September 7, 2020

Florida City Replaces Images of Black Former Fire Chiefs with White Faces. Two Fired...

Boynton Beach removes 2 officials after public art mural replaced images of black former chiefs with white faces

BOYNTON BEACH - After a public art project based on photographs replaced the images of two black former department chiefs with white faces, City Manager Lori LaVerriere removed Matthew Petty, the city’s fire chief, and fired Debby Coles-Dobay, the city’s public arts manager.

LaVerriere wrote in a Saturday afternoon statement that she “concluded a preliminary investigation regarding the inappropriate decisions made by City employees.”

Coles-Dobay wrote Saturday to the Post that she “was pressured to make this artwork change by the Fire Chief and his staff, as the City well knows.”

Coles-Dobay did not elaborate.

The removals are effective immediately. Petty, who initially faced demotion, agreed to resign, LaVerriere said in an email statement.

The mural, which the city unveiled this month, erased the image of Boynton-born and -raised Latosha Clemons, who was the city’s first and only black female firefighter and deputy chief.

She scaled and led the department ranks for about 24 years until retiring effective March 1.

The mural also erased the face of Glenn Joseph, the city’s former fire chief and the first black firefighter in Boca Raton’s department.

Officials removed the public art project a day after it was unveiled.

“I’m hurt. I’m disappointed. I’m outraged,” Clemons said Friday. “It’s been my heart and soul and my lifeblood to serve in the community where I grew up ... this is beyond disrespect and I basically want to know why it happened...”

Another day in the life in these increasingly vile times...

September 7, 2020

Re-Envisioning Sanitation As a Human-Derived Resource System

The paper I'll discuss in this post is this one: Re-Envisioning Sanitation As a Human-Derived Resource System (John T. Trimmer,* Daniel C. Miller, Diana M. Byrne, Hannah A. C. Lohman, Noble Banadda, Katherine Baylis, Sherri M. Cook, Roland D. Cusick, Fulgensio Jjuuko, Andrew J. Margenot, Assata Zerai, and Jeremy S. Guest, Environ. Sci. Technol. 2020, 54, 10446?10459)

This is an interdisciplinary paper, the authors include Civil and Environmental Engineers, Agricultural & Crop scientists and economists, Natural Resource Scientists, Biosystems Engineers, a representative of a human development organization, and a sociologist. All but two of the authors are based at various institutions in the United States, two of the authors are based in Africa, one from Makerere University in Kampala, the other at the Community Integrated Development Initiative, also in Kampala.

It is also a policy paper, not a research paper - scientists suggesting policy in review of the associated science - which obviously has no meaning now, but in a better, saner world, would have meaning. Science and facts would matter.

(I wish the world were more like those 1950's Japanese monster movies where national emergencies, usually represented by the frat boy behavior of the members of the Godzilla Clan (Godzilla, Rodan, Mothra, Gamera...etc) with respect to power lines, would involve political figures calling on scientists, and doing whatever it was that scientists advised to deal with the monster emergency.)

The big monsters today are much worse than Godzilla and friends wading through the wires coming out of substations; they are air pollution, climate change, and Covid-19, listed in order of likely associated daily death tolls. The science of all three are easily swamped by public opinion, which is another monster which most of time can also be described as "ignorance unchained."

Right now, according to the World Health Organization, from which the orange racist national ignoramus, the "President" of the United States has caused us to abandon, about 2 billion people lack access to improved sanitation. I often discuss this state of affairs when remarking on the more than 3 trillion dollars that has been squandered on so called "renewable energy" since 2004, with the result that the rate of climate change is increasing not decreasing. We're not doing as well as those Japanese scientists recommending procedures to deal with Rodan.

About 300,000 people under the age of 5 die from diseases associated with inadequate sanitation, or about 820 a day. This is dwarfed by the number of people killed by air pollution every day (about 19,000 people per day) but still...but still...

Source: UNEP/Bloomberg Global Investment in Renewable Energy, 2019

Annual Mean Growth Rate for Carbon Dioxide Concentrations, Mauna Loa CO2 observatory, Hawaii

WHO fact sheet: Sanitation and Health

Decades ago, when I abandoned my parents politics and became a political liberal, liberalism included a huge concern for the impoverished, not just in the United States, but elsewhere. Today liberalism seems increasingly to include things like worshipping Elon Musk and his car for millionaires and billionaires and the conversion of the continental shelf and huge tracks of wilderness into industrial parks for wind turbines, but I think, there is still some interest in human development goals on the left, I think. I certainly hope so.

One thing that should concern environmentalists, agricultural scientists, human development workers, and in fact, everyone on Earth who cares about the future - not that many people do these days - is the disruption of, and likely collapse of, the phosphorous cycle.

Phosphorous is not a so called "renewable resource." All of the world's agricultural productivity is very much dependent on mined phosphate rock which is rapidly being depleted.

A subject addressed in this paper, among others, is phosphorous flows, since phosphorous is one of the valuable components of human fecal waste.

From the paper's introduction:

Globally, over two billion people lack basic sanitation access, and even more use systems that do not safely manage human excreta.(1,2) Progress toward the Sustainable Development Goal (SDG) of universal sanitation coverage by 2030 remains limited: of 123 countries with <95% basic sanitation coverage, only 14 are on track for universal coverage.(1) In resource-limited communities characterized by poverty, poor infrastructure, and constrained access to food, water, and other basic needs, high failure rates plague sanitation systems, leading to increased environmental and human health risks.(3,4) Simultaneously, global agriculture continues to consume finite nutrient resources (e.g., phosphate rock) while large quantities of phosphorus and anthropogenically fixed reactive nitrogen are discharged to pollute aquatic environments.(5,6)

Recovering human-derived resources from sanitation (e.g., water, nutrients, organic matter from bodily excreta) has the potential to offset treatment costs, substitute for expensive or nonlocal inputs (e.g., synthetic fertilizers, polyhydroxyalkanoates), and improve resource access for populations facing financial or productivity constraints.(7?9) Recent research and policy efforts, particularly those associated with sustainable and circular economies, have promoted shifts from pollutant removal to resource-oriented management.(9?12) However, although technology options are rapidly expanding, multiple socioeconomic, environmental, and engineering challenges coconstrain sanitation-based resource recovery efforts (e.g., economic viability of recovery, market potential, and consumer acceptance of products).(9,13?16) Recognizing these challenges, sanitation research is becoming more interdisciplinary and incorporating broader stakeholder involvement. Consequently, many studies have developed and applied models, tools, and approaches linking sanitation with social, environmental, and resource systems, with the goal of examining multiple dimensions of sustainability and supporting decision-making.(14?31) Work in Mexico City, for example, linked social acceptance (through participatory scenario development) with environmental outcomes (through resource flow analysis) to evaluate water and sanitation possibilities.(32) More generally, authors have used nutrient recovery to reframe sanitation as an overlooked component of food and farming systems.(10,33) Others have noted the importance of integrating economic, social, and engineering systems to ensure the effectiveness of natural wastewater treatment systems (e.g., constructed wetlands, lagoons), particularly concerning pathogen control and human health protection.(34) The phosphorus cycle has received particular attention,(35?39) and human-derived phosphorus recovery pathways were recently reviewed from an integrated social, ecological, and technical perspective.(40)...

...Sanitation represents an interface between society and nature. It is an integrated system that can be both beneficial, through human-derived resources recirculated toward positive use, and detrimental, when improper disposal degrades natural resources (Figure 1). Beyond sanitation, efforts to analyze coupled human and natural systems have been underway for over a decade.(46,49,50) Scholars have developed a generalized social-ecological systems (SES) framework,(41,44,51,52) which emerged from studying governance of common-pool resources (e.g., forests, irrigation systems, fish stocks)(53) and has been tested in many contexts.(42,54?60)...

This is a rather long paper, covering a broad range of practical and technical issues and I cannot discuss everything that is in it at this time, but it is an important paper of the type that I think is critical to sustainability and is, as public policy goes today, being almost completely ignored: Waste to resource, which is something that all life on Earth worked by until disrupted by anthropogenic practices, largely associated with industrialization. Restoration of sustainability, in my opinion, need not ban industrial practices, but it should to the maximum extent depend on closed waste to resource cycles. All I can do in the present case is to offer up some graphics and captions from the paper. Interested parties can seek out the full paper through academic institutions - when and if they are reopened for use by the general public - or by subscription.

Pictures from the paper:

The introductory cartoon:

Graphics from the text:

The caption:

Figure 1. Illustrative components of human-derived resource systems. Sanitation can function as an interface connecting multiple aspects of social, ecological, and resource systems. These linkages can be positive, as in cases where resources (water, organics, nutrients) are recovered and recirculated toward beneficial uses, or negative, as in cases where disposal displaces resources, contaminating environments and degrading ecosystem services.

The caption:

Figure 2. The sanitation social-ecological systems (S-SES) framework. (a) The diagram shows the seven first-tier variables (also called core subsystems; e.g., sanitation, actors, related ecosystems) of the S-SES framework and includes distinct categories (second-tier variables; e.g., technology selection, sanitation users, water) within each core subsystem. The framework structure extends beyond the first and second tiers to provide additional layers of detail as needed; structured lists of third- and fourth-tier variables can be found in SI Tables S1–S7. (b) Flows of human-derived resources through the core subsystems of the S-SES framework suggest how the safety and accessibility of resources may change as they move through various stages. Appropriate management, treatment, and recovery strategies, implemented by actors operating within a policy and regulatory environment defined by governance institutions, can increase safety and minimize risks associated with recovered resources. However, these processes may introduce constraints on access related to technology availability, economic resources, and knowledge of sanitation and hygiene.

The supplemental information should be available for free at the link to the parent paper at another link therein.

The caption:

Figure 3. An illustration of the framework’s multitiered structure, using the sanitation subsystem as an example. The sanitation subsystem is expanded into four second-tier variables. Of these, we further expand technology and system selection (SAN.T) and outcomes (SAN.O) to show nested third-tier variables (the other two second-tier variables also contain lower tiers not pictured here). Two third-tier variables are then expanded to the fourth tier. For all core subsystems, full structured lists showing four tiers of variables can be found in SI Tables S1–S7. Additional variables, in levels beyond the fourth tier, can offer even greater levels of system detail and contextual depth. As they are likely to become increasingly context-dependent, we have not specified variables beyond the fourth tier. On the left, we show how a tiered structure is important when developing a shared vision and lexicon. Many studies may benefit from high levels of generality or precision, but finding a balance is important for effective interdisciplinary communication. Otherwise, researchers may remain trapped within existing boundaries by keeping other topic areas too vague or being too dependent on implicit disciplinary assumptions. A multitiered conceptual framing can help researchers speak to others with different perspectives, balancing these two extremes at midlevel tiers. Researchers can delve deeper to identify key aspects of ancillary topics, or translate specialized results to identify generalizable knowledge, typologies, and guiding principles.

The caption:

Figure 4. The changing nature of human-derived resources. This figure illustrates how a conceptual framework can provide an integrated lens across disciplines and concepts, suggesting new ways of understanding sanitation that can then be studied further. Here, we show a synthesis that arose organically as we developed the framework and allowed it to influence our own thinking. Integrating ideas from fields including economics, natural resources, and health, we considered how different types of reuse pathways change the nature of human-derived resources. Specifically, we consider the types of goods these resources represent, as defined by their excludability (i.e., the degree to which actors can be barred from using the resource) and rivalry (also called subtractability; i.e., the degree to which resource use diminishes the quantity or quality of the remaining supply). Sanitation systems manage and treat bodily excreta to reduce risks associated with reuse or disposal, but limited access to technologies, economic resources, and knowledge regarding appropriate strategies can function to exclude vulnerable populations. Advanced recovery processes that generate more expensive, higher-value products (private goods) may further increase excludability. Alternatively, other pathways (for example, those connected with ecosystem services) may generate common-pool resources (e.g., provisioning of forests or fish stocks) or public goods (e.g., regulation of water or air quality). In the interest of completeness, the figure includes club goods—the fourth general category of goods, defined by high excludability but low rivalry—although this category does not enter directly into our discussion of human-derived resources.

I trust you are enjoying Labor Day safely.

September 6, 2020

Grid Scale Life Cycle Analysis of Greenhouse Gas Implications of "Renewable Energy," and E Storage.

The paper I'll discuss in this post is this one: Grid-Scale Life Cycle Greenhouse Gas Implications of Renewable, Storage, and Carbon Pricing Options (Sarah M. Jordaan, Qingyu Xu, and Benjamin F. Hobbs, Environ. Sci. Technol. 2020, 54, 17, 10435–10445). The authors' institution is Johns Hopkins University.

We are now half a century into the grand experiment in which humanity first cheered for, then funded research on, then spent trillions of dollars on, and then bet the future of the planet on, so called "renewable energy." This was not, of course, the first time that the world had experienced a world built around "renewable energy." In fact, the world had survived upon renewable energy for many thousands of years, but abandoned it beginning in the early 19th century because as the world population grew, the vast majority of people, even more so than today, lived short miserable lives of dire poverty mired in ignorance and peasantry.

The exploitation of dangerous fossil fuels - the waste of which is currently rapidly destroying the planet - led to the creation, in many countries, of an industrial culture that ultimately led to the creation of a middle class, although vast pockets of dire poverty continued and still continue to exist. If you are reading this text on a computer - and it's difficult to imagine there is any other option for you to do so, no one prints the trash I write - you are a participant in that still existing and active industrial culture.

When I was a kid, I hoped to get good enough with German that I could translate Goethe's Faust. I never got there and went on to other things, but thinking about Faust now, it does seem that having been written at the end of the 18th century, Gothe certainly presaged the 19th and 20th centuries.

Du flehst erathmend mich zu schauen,
Meine Stimme zu hören, mein Antlitz zu sehn,
Mich neigt dein mächtig Seelenflehn,
Da bin ich! – Welch erbärmlich Grauen
Faßt Uebermenschen dich! Wo ist der Seele Ruf?
Wo ist die Brust? die eine Welt in sich erschuf,
Und trug und hegte; die mit Freudebeben
Erschwoll, sich uns, den Geistern, gleich zu heben.
Wo bist du, Faust? deß Stimme mir erklang,
Der sich an mich mit allen Kräften drang?

For the last 50 years there has been a broad, and now generally accepted, claim that the industrial culture could be maintained by a reactionary return to so called "renewable energy." So called "renewable energy" of course, never completely disappeared. The most successful form of so called "renewable energy" is of course hydro energy. In the early 19th century, many of the textile plants in say, New England (and elsewhere), as well as grain mills, relied on the use of hydromechanically driven machinery, water wheels, and of course, later on, on an increasingly massive scale, dams to generate electricity, hydroelectricity.

We are fresh out of major rivers to destroy, however, more or less.

The reactionary view that the world should adapt its industrial culture to so called "renewable energy" - which needed to be abandoned to build that culture in the first place - has, for most of its history, had little interest in the displacement of dangerous fossil fuels, but was more interested in preventing the rise of the only more or less infinitely scalable form of energy ever discovered on this planet, nuclear energy.

Over the years, having spent my life trying to understand things on the deepest level my tiny little mind is capable of reaching, I've looked into the origins of the anti-nuclear movement, a movement that is, in my opinion, killing people and killing the world.

In my generation, of course, there was some rationale for the anti-nuclear movement in the times of my childhood, a rationale that was far more emotional than practical. During the 1950's various countries around the world, with the United States and the former Soviet Union being the most egregious participants, engaged in ever more stupidly testosterone driven exercises in open air nuclear testing, culminating in the absurd "Tsar Bomba" nuclear test on the Soviet arctic island of Novaya Zemlya. Many people my age can remember huddling under their desks at school, famously ducking and covering, to survive a nuclear blast. In October of 1962, two testosterone driven world leaders, John F. Kennedy and Nikita Khrushchev nearly stumbled into vaporizing their countries.

This actually happened.

Another correspondent wrote about Tsar Bomba a short while ago in this space. It is here: Russia Just Declassified Footage of The Most Powerful Nuclear Bomb Blast in History

Long ago and far away, I also wrote about it as well: Every Cloud Has A Silver Lining, Even Mushroom Clouds: Cs-137 and Watching the Soil Die.

The argument against open air nuclear testing was greatly (and correctly) advanced by noting that such testing widely distributed radioactive materials throughout the atmosphere, where it settled on land and into the sea. Those radioactive materials are still here by the way. The half-life of cesium-137 is 30.167 years. This means that as of this writing, in 2020, about 26.99% of it still remains. In my post of 11 years ago, I noted that this radioactive cesium has value in helping people track the erosion of soils.

I very much recall growing up fearing the element cesium - I was certainly aware of it in elementary school I was probably in my late teens before I realized that there was cesium that was not radioactive.

Welch erbärmlich Grauen Faßt Uebermenschen dich!

What horror grasps you, you superman!

Funny...funny...today, as an old man nearing the end of my life, I'm rather fond of cesium isotopes, thinking they might do great things for the humans that come after me. I wish we had more of the stuff, not less. I think quite a bit about cesium, even more than I did in elementary school, when it terrified me. That's just me though. But yes, I was a child once.

It turns out, as I learned reading an obscure book that was on the shelves of either one of Rutgers University's libraries or Princeton University's libraries that one place the early anti-nuclear power movement got its birth was very near where I grew up cowering in fear of cesium-137, on Long Island.

When I was a boy the power company on Long Island was called LILCO, the Long Island Lighting Company. In the late 1950's LILCO announced plans to build three nuclear power plants, one at Jamesport, on the Eastern North Fork, one at Shoreham, and one in Lloyd's Neck.

The one to which I lived closest was on Lloyd's Neck. In these times, no one would try to build any kind of industrial facility in a place like Lloyd's Neck. It's where wealthy people live, very wealthy people. Although I grew up less than 10 miles away, I never felt like I could even set foot in Lloyd's Neck when I was growing up, although I did once go to a house there. My best friend's girlfriend's Mom was a maid in one of them, and one time when she was sick, her daughter, my friend's girlfriend, asked my friend and I to drive her up to the house so she could clean the house so her mother wouldn't get fired. The owners went away, and we all went in to clean the house. It had an indoor swimming pool. "Wow!" We said. "Wow!" Before then, we didn't know that people could afford something like that.

Rich people don't like industrial facilities in their neighborhood. They bring traffic, and roads and pollution, and well, poor people who aren't maids. The people living in Lloyd's Neck had lots of resources, and pointed out that there was something called "nuclear waste" and it contained exactly the same kind of stuff that came out of Tsar Bomba, the American "Big Mike" and Bravo and oodles of other nuclear bombs. It was unsafe, they said.

So LILCO, understanding that rich people are essential for all life on Earth, cancelled the Lloyd's Neck plans pretty damn quick, but built Shoreham, which built on the momentum of fear of nuclear materials established by the good folks in Lloyd's Neck, but built Shoreham, which generated lots of "exposes" by Newsday, so that Jamesport was cancelled and Shoreham, although completed and having undergone preliminary critcality testing, never operated, was sold to New York State for one dollar, which shut the plant permanently. LILCO went bankrupt.

Let me tell you something: People died because Shoreham didn't operate. They died from air pollution, dangerous fossil fuel waste that actually has a long history of killing people.

As a young man, I was among those who demonstrated against Shoreham. History will not forgive me, nor should it.

So we bet the planet on the reactionary vision that our industrial culture could survive on so called "renewable energy." Of course it hasn't done so, and it isn't doing so, but we still hear any that word quite a bit about what so called "renewable energy" could do. It's 2020. I've been personally hearing - and for a long time believing - that so called "renewable energy" could power the world.

My whole life...my whole life...

I am personally running out of time, and all those prayers in which I used to believe, prayers about the coming renewable energy nirvana will be "lost, in time."

They weren't honest prayers in any case, reactionary as they were, inasmuch as they were completely uninformed prayers, more mysticism than fact.

Since we have bet the planetary atmosphere on so called renewable energy, one would think that we really, really, have thought the whole thing through on a grand scale.

If one spends a lot of time poring through the scientific literature - something I routinely have been doing for decades - one can come across thousands upon thousands of papers in various journals all about so called "renewable energy." I've read through a significant number of them over the years, certainly, at various levels of depth, thousands of them. Almost uniformly the opening sections of these scientific papers speak - it's a cultural imperative almost everywhere on the planet - in praise of so called "renewable energy." Increasingly one sees here and there, a few examples of dissidence with respect to the decided point that vast amounts of money and effort should be thrown at "renewable energy," - I am less alone in this than I used to be - but overall the papers speak in positive terms. One hears the same stuff that one hears in the general public, how the price of so called "renewable energy" is falling so that it now "cheap," how the use of so called "renewable energy" represents a strategy for addressing the climate crisis caused by dangerous fossil fuel waste, how so called "renewable energy" is sustainable, and of course, how fast so called "renewable energy" is growing. Although these claims widely published in magical "peer reviewed" papers - "peer review" is allegedly magical and somehow not subject to the flaws and frailty of humanity, cultural and otherwise - I contend that all of these statements are either disingenuous, counterfactual, dishonest, or in some cases, outright delusional.

Anyway, you would think, having bet the future of the planetary atmosphere on a reactionary return to the use of so called "renewable energy" to support all of humanity's needs, that the effects on scale , a grand scale that the whole thing had been well thought through, even though the decision to abandon renewable energy and replace it first with dangerous coal, then with dangerous coal and dangerous petroleum, and finally with coal, petroleum and (most recently) dangerous natural gas was never thought through, was it?

According to the authors of this paper, however, even on the scale of large electric grids, the situation was not well thought through.

They write:

Climate change is among the most pressing challenges for the electric sector, due to the prominence of fossil fuels in the present generation fleet. While the U.S. power sector has experienced substantial emissions reductions in recent years, fossil fuels were still the dominant source of electricity at 63.5% of generation in 2018, with 35.1% of generation fueled by natural gas and 27.4% fueled by coal.(1) The grid has been changing not only from coal to gas but also with a growing portion of intermittent renewables: wind and solar PV have grown from 55000 to 272000 Gigawatt-hours per year (GWh/year) and 76 to 60000 GWh/year, respectively, from 2008 to 2018.(2) Provided that the costs of renewable technologies continue to fall, energy storage is broadly considered one of the most attractive solutions with notable potential to balance the intermittency of variable renewable power (namely, wind and solar). The true environmental benefits of new storage capacity are challenging to discern due to the overall dynamic interactions between power plants and storage inherent to the operations of an electric grid, particularly in comparison to policy options such as carbon pricing. But generation is only one part of the life cycle of power systems: the life cycle includes additional processes, such as materials extraction to construct power plants, upstream fuel extraction (where applicable), operations, and transmission of the electricity to consumers. Our analysis addresses these challenges with an examination of grid-scale greenhouse gas emissions through an integrated analysis of optimized technology-policy scenarios that captures the full supply chain implications.

Life cycle assessment (LCA) provides a robust method for examining these upstream and downstream emissions as a cradle-to-grave approach to quantifying the environmental burdens of products or processes from materials extraction to waste disposal (cradle to grave).(3,4) Present emissions models, however, are limited in their capability to estimate life cycle emissions changes at subnational scales and hourly time steps.(5,6) When quantifying the life cycle emissions of an electricity grid, national assumptions about the generation mixes are typically applied, neglecting to account for the regionalized differences and temporal dynamics implicit to power systems that can result in variable emissions results.(7) Similar challenges have been noted for other air pollutants(8,9) and water consumption.(10?13) Data that characterize dynamic grid interactions can result in more realistic life cycle emissions and nuanced understanding of their spatial and temporal distributions, but that requires that LCAs leverage information at more refined spatiotemporal resolutions.(14?16)

To the authors’ knowledge, there has yet to be a comprehensive evaluation of the life cycle emissions associated with different configurations of renewable capacity additions, storage capacity additions, and carbon pricing options at the scale of grids (i.e., rather than individual technologies). In order to perform such an evaluation, robust methods must model the life cycle environmental and economic impacts of such changes at the grid-scale. A review of models that estimate the emissions of grid operations uncovers two approaches: (1) use of historical data or (2) use of power systems and market models based on optimization methods.(6) In this paper, the latter approach is taken because a focus will be on the synergistic impact of low-carbon technologies (i.e., storage and renewables) and market mechanisms (in this case, carbon prices) for which there is a lack of relevant historical data.

I have added the bold. As for their disclaimer, "To the authors' knowledge..." it is in accordance with my own view, but it seems to me that there is real evidence for the claim that there has yet to be a "comprehensive evaluation," inasmuch the oft repeated disingenuous statement that "renewable energy is cheaper than coal..." (...or gas, or oil, or nuclear...) doesn't ever refer to when it is cheaper and what the value of energy might actually be on those occasions that it is cheaper.

At midnight a solar cells is of course a stranded asset with zero value. One should however also ask - and few people ever do - whether a solar cell has any value when it producing near peak energy if and when - this actually happens - the price of wholesale electricity is zero or less than zero, the low prices realized because electricity being produced copiously by so called "renewable energy" at a time when no one actually needs it. Consideration of this question might go a long way to explaining why the highest consumer electricity prices in the OECD are found in Denmark and Germany.

To offer a word on the "growth" of wind and solar power as described in the text, which happily is not, described - as it so often is on "green energy" websites hyping these forms of energy - as "spectacular, usually along with rather innumerate "percent talk," let me repeat the operative phrase above:

The grid has been changing not only from coal to gas but also with a growing portion of intermittent renewables: wind and solar PV have grown from 55000 to 272000 Gigawatt-hours per year (GWh/year) and 76 to 60000 GWh/year, respectively, from 2008 to 2018.

In "percent talk" this can, again, disingenuously, made to sound spectacular. Being familiar with this type of misleading rhetoric, here's how this horseshit would likely sound: Solar Energy production from 2008 to 2018 grew by almost 79,000%!!!! Wind energy production grew by almost 500%!!!!

A GigaWatt-hour (GWh) is a unit of energy, not a unit of power that is so often used to justify the disaster that so called "renewable energy" represents, by pretending that peak power is the equivalent of average continuous power. One GWh is equal (exactly) to 3.6 trillion joules. It follows that 272,000 GWh is the equivalent of 979 petaJoules, or 0.979 exaJoules. Similarly, 60,000 GWh is the equivalent of 217 petaJoules or 0.217 petaJoules. Given the number of seconds in a sideral year, 31,557,600 seconds, this translates to an average continuous power of 31,300 MW for wind, and 6,900 MW for solar. Overall, this is the equivalent of about 37 average size power plants capable of operating continuously, for example, nuclear plants.

This sounds great, until one recognizes that neither solar nor wind actually produce continuous power, nor is the power they produce actually even produced in any kind of synchronization with demand. Their production is, in fact, subject to the vicissitudes of weather. This means in theory, one needs 31,300 MW of redundant power capacity to back up wind, and 6.9 MW of redundant power capacity to back up solar. If that capacity does not exist, then the system crashes and there is not enough power to serve all customers; a situation recently observed in portions of the very grid that the paper discusses.
Recently. Very recently. During a heat wave. A heat wave that almost certainly took place because climate change has not being addressed and isn't being addressed.

Yeah...yeah...yeah...I know...batteries, batteries, batteries…batteries will save the world, in the same way so called “renewable energy” saved the world, which – looking at CO2 concentrations in the atmosphere as of yesterday, it didn’t.
Most renewable energy advocates turn into that appalling and dangerous idiot Ayn Rand when the cost of nuclear power plants are discussed. Thankfully that idiotic old biddy Ayn Rand kicked off, although many of the poor thinkers who embraced her cartoonish view of the world are regrettably still with us, acting, in fact, on her stupidity and venality, the view that selfishness can be ethically excused among the social animals that human beings represent. Ayn Rand is dead, but her conceits are still killing people. So, I claim, will the conceits about batteries, a subject the authors' discuss in the paper under discussion.

By contrast, if we were less Randian, and thus bothered to care for future generations, and thus spent money to build infrastructure that would serve future generations rather than our own – in other words did something for which there was little in it for us but lots in it for humanity – we would build nuclear plants. The primitive technology of the 1950’s, constructed using primitive computational devices, built nuclear reactors that demonstrably worked for better than half a century; it is now understood that we can design and build them to last decades longer.

I say this a lot: A nuclear power plant is a gift from one generation to another. My father’s generation built the Oyster Creek nuclear power plant, and for nearly twenty years of my life, it kept the lights on where I live in New Jersey without causing a single loss of life.

There is no record of batteries lasting half a century; even the most advanced are converted into electronic waste in ten to twenty years. This means that infants born today will, as young adults, assume responsibility for disposing of this stuff; and no, there is no real infrastructure or technology for cheaply and easily doing even that, despite all the glib hand waving rhetoric one sees and hears.
Anyway, the authors discuss a large area that has significant so called “renewable energy” infrastructure, and little nuclear structure. As is the case with all “renewable energy” paradises, the largest single portion of energy is comprised of dangerous fossil fuels: In this grid dangerous natural gas comprise 40.5% of the capacity, “only” according to the authors “40.5%.” This is slightly more than the largest form of so called “renewable energy,” hydroelectric dams, and includes those that represent an assault on, for just one example, salmon, as well as that which converted the Colorado River Delta ecosystem into a desert, where, as of this writing September 6, 2020, according to the forecasted temperature in Yuma Arizona is expected to peak at 47oC (114 oF).

We are, I think, more or less out of additional major rivers to destroy.

Peak electricity demand generally takes place in the late afternoon, early evening. In a post here that was essentially pure data with very brief commentary, I showed the hour highest power peak demands in California in July of 2019:

Hours of the Top 50 CAISO Electricity Loads in California, July 2019.

Here is the salient part of the commentary minus the sarcasm:

The first column is the power demand; the second is the ranking of the demand, and the last is the hour of the demand (on a 24 hour clock.)

It seems the top ten all took place in the early evening hours, while among the top 20, 6 occurred in the late afternoon, with the other 14 being in the early evening.

Here is real time data collected from the CAISO site at around 6:10 pm EST, 3:10 PST September 6, 2020 on California's Energy demand live and projected for the day, and supply both current and throughout the period beginning at noon on this date:

(Because of an error in preparing the graphics file for this post, the line supply graphic immediatly above was recorded at 4:00 pm PST, 7:00 EST.)

This data can be accessed (in real time) here: CAISO Today's Outlook

It appears the wind isn't blowing all that strongly today, but there's plenty of sunshine. There are people however, that as the day proceeds, and the power requirements climb to a significant portion of total system capacity, the sun will, um, go down. I tend to believe these people, owing to the experience of having lived in California. In fact, this seems to take place everywhere, earlier in the winter than in summer.

All of this is relevant since the authors are writing about a grid that includes California. They write:

The study area is the Western Interconnection comprising the western geographic area of North America, where the grid is synchronously operated (Figure 1).(39) Of the United States, all of Arizona, California, Colorado, Idaho, Nevada, Oregon, Utah, and Washington are part of this interconnection in addition to parts of Montana, Nebraska, New Mexico, South Dakota, Texas, and Wyoming. Parts of Northern Mexico are included in addition to the Canadian provinces of British Columbia and Alberta. While coal and natural gas remain strong contributors to the region’s power supply, they combined represent only 40.5% of the 249 GW of the region’s generating capacity.(40) Of the total capacity, hydroelectric power ranks first at 38.2%, followed by natural gas (27.4%), coal (13.3%), nuclear (8.5%), wind (6.6%), solar (3.1%), geothermal (1.9%), and other sources (1.2%). The Western Interconnection was selected as the study region due to its importance to Western North America: it serves 80 million people and spans more than 1.8 million square miles.(41) Further, a series of recent efforts have resulted in vetted optimization scenarios that examine the influence of different renewable-storage-policy configurations with the JHSMINE model, created in collaboration with the Western Electricity Coordinating Council (WECC).

Figure 1:

The caption:

Figure 1. Map of JHSMINE reduced 300-bus network of Western Electricity Coordinating Council of North America. Dots represent nodes of the grid, and triangles represent the location where new renewable generation can be sited. Red/Orange lines are existing AC/DC lines, and blue lines are equivalent lines that are results of the network reduction.

(The blue lines are apparently computational artifacts to reduce computational complexity and thus computer time, thus they are virtual power lines, nor real power lines.)

This next graphic is very important I think, since it delineates the system boundaries for the calculations.

The caption:

Figure 2. Simplified scope of the grid-scale LCA, with systems boundaries for each technology based on NREL’s harmonization studies.(17,46?51) Life cycle emissions are estimated using NREL harmonization data for each type of generation modeled in JHSMINE, adjusted for each power plant’s operational efficiency using their heat rates. Results from the JHSMINE model determine the optimized interactions between energy types and storage on the grid, under 21 scenarios of renewable energy, storage, and carbon pricing options. Our analysis and discussion focus primarily on upstream emissions as NREL’s harmonization studies found that emissions impacts are weighted toward the upstream.

Some commentary: The cost of "turbine manufacture" should not exclude mining - although it is not clear whether or not it is included in manufacturing costs. A major component of a wind turbine system is steel, and the manufacture of steel in turn, depends very much on mining both iron ore and more importantly coal. The amount of steel required to construct, and for that matter to replace wind infrastructure depends sensitively on the lifetime of these devices. Data from the comprehensive master register of wind turbines maintained by the Danish Energy Agency, which I have analyzed elsewhere multiple times suggests that the average lifetime of a wind turbine is slightly less than 18 years. In addition, it must be clearly stated that the environmental impact carbon and otherwise of magnets is something of a black box, since almost all of the neodymium and dysprosium in the world is mined in China and it is well known that besides extraction from the minerals, solvent extraction techniques for lanthanide separations are dependent on dangerous fossil fuel based solvents.

Secondly, uranium mining is still required to run the existing nuclear infrastructure, although the disassembly of Soviet and American nuclear weapons negotiated by Al Gore in the 1990's did lead to a temporary decline in this requirement, regrettably not including plutonium. However, the most recently approved nuclear reactor in the United States, the Nuscale reactor, I believe is a "breed and burn" reactor of a type that, with wise use of plutonium, suggests that a need for uranium mining can (and should) be eliminated for centuries, since the uranium (and thorium) already mined is sufficient to supply all human energy needs for centuries without the use of a single piece of coal, a single kg of natural gas, a single liter of oil. There is no effort to exploit this possibility, nonetheless it is real.

The next graphic points out, very clearly, the carbon cost of nuclear energy, as well as various other schemes for producing energy, and importantly for storing energy by various technologies:

The caption:

Figure 3. (a, b) Life cycle results for individual technologies compared to grid-scale scenarios. Individual technologies for comparison include coal, petroleum, natural gas combustion turbine (GasCT), combined cycle natural gas (CCGT), concentrating solar power (SolarThermal), solar photovoltaic (solarPV), wind and geothermal (Geo). Scenarios include different configurations of storage additions (Pumped Hydro (PH), Compressed Air Energy Storage (CAES), and Battery Energy Storage Systems (BESS)), new wind capacity, and different prices on carbon dioxide (none, $20/tCO2, $58/tCO2, $100/tCO2) (see Table 1). Part a compares the grid-scale LCA results to life cycle results for individual technologies. Part b shows more clearly the results for the grid-scale scenarios. Note that these results are based on the aggregate power plants using annual estimates.

Note that this graphic, consistent with many other papers written on this topic clearly shows that in terms of carbon cost, nuclear power is lower than solar PV, lower than solar thermal, lower than geothermal, and comparable with wind power when the wind is blowing. No matter what technology is utilized to store wind (or solar) energy, the carbon cost is significantly worse than nuclear power.

The big, big, big, big, big difference between nuclear and solar and wind, however is that nuclear energy is reliable. Above I noted that to cover the average continuous power of solar and wind energy on the grid described herein, in fact, 62 MW of power at a mininum.

An typical nuclear power plant most common in the US operates at about 33% thermal efficiency, producing about 3000 MW thermal, 1000 MWe. This means to displace 31,000 MW of so called "renewable energy" and the 31,000 MW of redundant power infrastructure (in reality, if not in fantasy, gas power) 31 nuclear plants of the type built in the 1970's using 1950's and 1960's technology would be required. Much of the thermal energy of nuclear fission is thus wasted. I have personally spent years convincing myself that the thermal efficiency of nuclear power plants could be more than doubled via strategies that take some of the techniques used by the dangerous natural gas industry, with respect to combined cycle performance, and that nuclear heat can be utilized to generate electricity when needed and to perform other tasks, including but hardly limited to making fuels and remediating the environmental disaster we have left for all future generations in absolute contempt for them.

I've discussed all of that, and will discuss more of that, elsewhere.

To close out the discussion of the paper, here's a little bit about the carbon cost of these grids, coupled to time, similar to the real time California data shown above:

The caption:

Figure 4. (a–d) Mean life cycle grid emissions for each scenario, estimated at hourly time steps for each of the four representative days modeled in JHSMINE.

At no point, do any of these "renewable energy/storage/carbon tax" scenarios produce electricity as cleanly as nuclear power does, as shown in figure 3 above.

If we gave a rat's ass about the future - clearly we don't - we'd cut the crap and face reality - but I doubt we will.

I hope you are enjoying the Labor Day holiday should you be fortunate enough to not be working during it. I would implore you to not behave as if the Covid crisis is over - it isn't - and thus to maintain all safety procedures consistent with your health and the health of others. Have a safe evening and a safe holiday!

September 4, 2020

Bats and Wind Farms: The Role and Importance of the Baltic Sea Countries...and Biodiversity...

The paper I'll discuss in this thread is this one: Bats and Wind Farms: The Role and Importance of the Baltic Sea Countries in the European Context of Power Transition and Biodiversity Conservation (Simon P. Gaultier,* Anna S. Blomberg, Asko Ijäs, Ville Vasko, Eero J. Vesterinen, Jon E. Brommer, and Thomas M. Lilley,* Environ. Sci. Technol. 2020, 54, 17, 10385–10398.)

This paper is open sourced under a creative commons license.

Bats of course, are getting a bad rap because of their unique immune systems which make them carriers for pathogenic virions . Still I rather regard them in the same way as I regard birds; which is to say they matter to me. I oppose their extinction.

Back in 2017, in this space, I appealed to a book in my personal library called Why Birds Matter. That post is here: A Minor Problem For Sound Science of the Effect of Offshore Windfarms on Seabirds: There Isn't Any.

I'm an old time environmentalist, in the John Muir tradition: I believe that environmentalism precludes, rather than encourages the transformation of pristine wilderness into industrial parks for energy production. Apparently my kind of environmentalism has gone out of fashion, but frankly, despite being somewhat unpopular, I'm not inclined to change my mind: I still agree with John Muir.

Denmark - bless their offshore oil and gas drilling souls - keeps a complete register of all its operating and all of its decommissioned wind turbines on land and at sea. It can be found here, in either English or Danish, your choice: Data for existing and deregistered facilities (end of 07 2020) - uploaded 31 August 2020

The most recent monthly production figures for all the operating wind turbines in Denmark - apparently over 6,200 of them as of this writing - in the period between June 20 and July 20, 30 days, was 1,307,912,614 kWh. This is approximately 4.708 petaJoules. This was a period of 30 days, and each day has 86,400 seconds in it. This means that average continuous power output, average, not (as is actually obtained) lumpy power output, was 1,817 MW for all the wind turbines in Denmark.

A typical nuclear power plant built on 1970's technology and still operating today - most nuclear power plants operate between 90% and 100% capacity utilization - will produce about 1000 MWe in a relatively small building. This means that two relatively small buildings containing nuclear reactors built on 1970's technology could produce reliably as much energy as all the wind turbines in Denmark, all 6,200+ of them.

...without killing seabirds...

...without killing bats...

Without requiring 6,200+ steel posts transported by huge trucks or huge barges powered by diesel fuel and made out of iron ore heated in coal fired blast furnaces containing coke made from coal by heating it coal fires.

Admittedly, my kind of environmentalism is out of fashion.

I only refer to the full article however. Again, it's open sourced. Anyone who gives a shit about bats, or birds, or about the fact that the trillions of dollars thrown at so called "renewable energy" has failed to address climate change, can read it for one's self.

Let me just say that I disagree with the first lines of the paper which read as follows:

Wind power is a valuable asset for energy transition as it is an efficient and sustainable way of producing energy.(1,2) Moreover, it generates near-zero greenhouse gas emissions during its operation in contrast to fossil fuels, and the approximate payback time for wind turbines in Europe is only a few months.(3,4) However, wind farms can have negative impacts on biodiversity, by destroying habitats during the construction phase and causing bird and bat mortality during the operating phase.(5,6) Bats (order: Chiroptera) are already facing numerous threats worldwide, and given their low reproductive output, it is vital to consider them in wind power development.(7,8)

Despite the first observations of wind turbines causing bat mortalities dating back to 1972,(9) serious questioning of the impacts of wind power on this taxa only emerged at the end of the twentieth century, with increasing observations of dead bats at wind farms.(10,11) Before this period, consideration of bats in wind farm projects was not mandatory, partly because of a general lack of knowledge on bats; thus, farms were constructed in areas that now would be considered inappropriate because of an associated high collision risk for bats. Research has now produced hundreds of studies, articles, and books on the phenomenon and its characteristics to help understand the impacts of wind farms on bats, and creating effective mitigation for current and future wind power.(12?18)
Our understanding of the topic is mainly based on studies from Central Europe and North America.(7,19) However, there is little knowledge on the impact of wind farms on bats in the European boreal biogeographic region, a part of the continent significantly different from Central Europe (Figure 1). Conditions vary with latitude but generally this region possesses shorter summers, less light, lower temperatures and precipitation, and a longer snow cover than the rest of Europe.(20,21) The European boreal biogeographic region is mostly covered by forests (60% of the area) or wetlands (8% in average, but it reaches 50% in the northern part of the region).(21)...

Wind power is not, in my view, "a valuable asset for energy transition." No "transition" is taking place. By appeal to raw data - something called "facts" - one can easily show that the wind and solar industries combined and including geothermal and tidal energy are growing much, much, much more slowly that the use of dangerous fossil fuels in this century.

The rate at which carbon dioxide, a dangerous fossil fuel waste, is accumulating in the atmosphere has reached as of 2020, a rate of 2.4 ppm/year, almost double the rate observed in the 20th century.

Nuclear plants built in the 1970's still operate. One can show that the lifetime of a wind turbine, by appeal to the aforementioned data tables at the Danish Energy Agency's wind turbine database, that the average lifetime of a Danish wind turbine is less than 18 years. This means, every twenty years, they all need to be replaced, on average, which is some measure, undoubtedly why they remain what they have always been; useless for the address of climate change; and useless for the arrest in the use of dangerous fossil fuels.

The paper concludes, after a fairly detailed discussion of the parameters connected with bat ecology and the industrialization of wild spaces to build "wind farms," thus:

The impacts of wind power on bats in Europe is a unique issue that requires more collaboration and standardization of research within the countries to resolve the problem because it affects the same species and sometimes the same populations across the continent. At the same time, Europe offers a great diversity of climate, biome, and habitats influencing species in a plethora of ways, resulting in significant differences in individuals of the same species whether they are located in Southwestern or Northeastern Europe. These differences need to be studied to obtain a better understanding of the various species or phenomena.
Unfortunately, the issue of the impacts of wind power on bats is still not entirely acknowledged in some countries, such as Estonia, Finland, Latvia, Lithuania, Russia, or Sweden. Data on bat biology and ecology are lacking and they are necessary if a comprehensive knowledge base is to be created with respect to the impacts of wind turbines and in order to solve the issue. A legal framework has also been delayed on the subject, most likely because of the missing data. All these requirements have to be addressed quickly because of the constant rise in the construction of wind farms in these countries, and above all, because of the important role Northeastern Europe has for bats.

.

Again, if interested, if "bats matter," you can read it yourself.

I trust you will enjoy the upcoming holiday weekend safely.

September 3, 2020

Separation of Scandium from HCl-Ethanol Leachate of Red Mud by a Supported Ionic Liquid.

The paper I'll discuss in this post is this one: Separation of Scandium from Hydrochloric Acid–Ethanol Leachate of Bauxite Residue by a Supported Ionic Liquid Phase (Dženita AvdibegovićDženita Avdibegović
and Koen Binnemans Ind. Eng. Chem. Res. 2020, 59, 34, 15332–15342)

Red Mud, also known as Bauxite residue is a troublesome side product of the aluminum industry which is primarily addressed by impoundment reservoirs, landfills, etc.

A recent news item in the journal Science discussed this problem and included this picture:

Red mud is piling up. Can scientists figure out what to do with it? (Service, Science Aug. 20, 2020).

Scandium is the first "d element" in the periodic table, but is often treated as if it were a lanthanide element, because of the closeness of its chemistry with the lanthanides; however there are no real concentrated ores of the element and thus, even though it is not particularly rare, it is very, very, very expensive, with prices in the thousands of dollars per kg. The element is strong, and light, much like its neighbor in the periodic table, titanium, for which plentiful ores (the wonder substance, TiO2) exist.

It is known that when scandium is alloyed with aluminum, it can greatly improve the strength of the metal.

The paper under discussion addresses the recovery of scandium from red mud. I am familiar with one of the authors, Dr. Binnemans as a result of a very nice review article he authored many years ago, owing to his expertise in the chemistry of ionic liquids with respect to the f elements, the lanthanides and actinides: Lanthanides and Actinides in Ionic Liquids (Binnemans, Chem. Rev. 2007, 107, 6, 2592–2614)

From the introduction to the more recent paper cited at the outset of this post:

Scandium is a scarce and expensive rare-earth element.(1) As a consequence, its commercial applications are still limited. Its major uses are in solid oxide fuel cells and as an alloying metal for aluminum. The addition of no more than 0.35–0.4% of scandium to aluminum alloys results in a material with superior mechanical strength.(2,3) Scandium is rarely found in nature in concentrated ore deposits but is obtained as a byproduct in the extraction processes of other metals such as the rare earths and uranium.(4)

Bauxite residue (BR) or red mud is an alkaline byproduct generated in the Bayer process for production of alumina from bauxite ore. Its global annual average production is estimated at 150 million tonnes.(5) It is commonly disposed by lagooning or “dry stacking” methods. In the lagooning method, BR slurry is pumped into storage ponds. BR disposed in such a way can create safety and environmental issues, such as contamination of surface and ground waters by leaching of alkaline liquor and other contaminants.(5) Dry stacking is used as the preferred method for BR disposal in order to reduce the potential for leakage of alkaline liquor and increase the recoveries of soda and alumina.(5) Both methods for disposal of BR require a substantial area of land, which could be used, for instance, for forests or agriculture. BR has attracted a lot of research attention in the past years as a resource for metals or as a building material.(6?12) BR can also be a valuable resource of scandium, but the scandium concentration is dependent on the type and origin of the bauxite ore.(13) For instance, Greek BR contains around 120 g tonne–1 of scandium, which is much higher than the average abundance of scandium in the Earth’s crust (22 g tonne–1) and high enough to consider this BR as a resource for scandium recovery. The main metals in BR are iron, aluminum, calcium, sodium, silicon, and titanium, and these elements are present in much higher concentrations than scandium.(14) Greek BR also contains other rare-earth elements (e.g., yttrium, lanthanum, neodymium) besides scandium, but their economic value in BR is much lower than that of scandium.

Typically, scandium is recovered from BR by hydrometallurgical methods or by a combination of pyrometallurgical and hydrometallurgical methods.(15) BR or its slag after a pyrometallurgical treatment is leached with mineral acids followed by recovery of the dissolved elements in the leachates by precipitation methods, solvent extraction, or ion exchange...(15?20)

...In the present study, the enhancement of the selectivity of sorbents for scandium is investigated by tuning the composition of the solvent in which scandium is dissolved. The selectivity for scandium over iron is investigated in batch mode from aqueous solutions and solutions with green, organic solvents (ethanol, 2-propanol, ethylene glycol, and polyethylene glycol 200). The investigated sorbents are a supported ionic liquid phase (SILP) betainium sulfonyl(trifluoromethanesulfonylimide) poly(styrene-co-divinylbenzene) [Hbet–STFSI–PS–DVB], bare silica (SiO2) and silica modified with ethylene diaminotetraacetic acid (SiO2–TMS–EDTA) (Figure 1). The SILP has been previously used to recover scandium from BR leachate with nitric acid.(17) Scandium was selectively eluted from the SILP column with dilute phosphoric acid, but the uptake of other major components of the BR leachate was also significant, which diminished the amount of leachate that could be processed. Therefore, an improvement in selectivity of the SILP by a solvometallurgical method is further investigated.

Figure 1:

The caption:

Figure 1. Sorbents tested for scandium recovery from BR leachates: (a) SILP Hbet–STFSI–PS–DVB, (b) silica, and (c) SiO2–TMS–EDTA.

An issue with red mud is that it generally contains quite a bit of iron, and therefore one must achieve selectivity in such a way that the scandium is highly concentrated and the iron rejected. (Since we are living future generations with the best ores depleted, it is possible that red mud will be another form of garbage than we leave them to sift through for materials.) Red mud also contains considerable sodium, which is why ethanol in HCl appears to be a fairly good solvent system for achieving separations:

The intrinsic selectivity of a sorbent for a given metal ion is influenced by several factors: (a) the mechanism of sorption, which is typically governed by the functional groups of sorbents, the coordination sphere, and the charge of metal ions, (b) the kinetics of the sorption, and (c) the sorption medium, including the presence of metal complexing agents. Here, the selectivity of the three sorbents (SILP, SiO2, and the SiO2–TMS–EDTA) was explored by variation of the sorption medium. The selective uptake of scandium was investigated from water, ethanol, isopropanol, ethylene glycol, and PEG-200 solutions containing scandium and iron in equimolar concentrations. In previous ion-exchange studies, it has been pointed out that scandium(III) and iron(III) separation from BR leachates is challenging because of the similar charge density of these ions and their similar hydration enthalpies.(18) As it is also one of the major elements in the leachate of BR, iron was chosen for the sorption studies as a competitive ion to scandium.
Both scandium and iron were nearly quantitatively sorbed by the SILP from their binary aqueous feed (Figure 2a). However, about 88% of scandium was recovered from the ethanolic feed by the SILP with a negligible amount of cosorbed iron. Moreover, the sorption of scandium was still higher (98%) than the sorption of iron (55%) even from the feed comprising ethanol and water in 1:1 volume ratio. The recovery of scandium and iron by the SILP takes place by exchange of their positively charged species in the feed for protons of the carboxyl-group of the SILP.(29) In aqueous acidic solutions of ScCl3 of concentration below 0.255 mol L–1, scandium is predominantly present as hexaaqua complex [Sc(H2O)6]3+. Neutral or anionic species like ScCl3, [ScCl4]?, or [ScCl6]3– are not formed, even in the presence of an excess of chloride ions.(30) Therefore, in the tested 1 mmol L–1 aqueous feed, scandium(III) is present as [Sc(H2O)6]3+ which is exchanged with the protons of the SILP.

SILP = (Supported Ionic Liquid Phase.)

Some more pictures from the text:

The caption:

Figure 2. Sorption (%) of scandium(III) and iron(III) from 2.5 mL of their 1 mmol L–1 aqueous, organic, and aqueous–organic mixtures of ethanol (EtOH), isopropanol (i-Pr), ethylene glycol (EG), and PEG-200 by 25 mg of the sorbents: (a) SILP, (b) SiO2, and (c) SiO2–TMS–EDTA. The 1:1 ethanol, 1:1 isopropanol, and 1:1 PEG-200 are feeds comprising water and the solvent in 1:1 ratio.

The caption:

Figure 3. Concentrations (mg L–1) of elements in the leachates of the Greek BR: (a) minor elements (scandium and yttrium) and (b) major elements (calcium, aluminum, sodium, silicon, titanium, and iron). The BR was leached with 0.7 mol L–1 HCl in water (aqueous leachate) or 0.7 mol L–1 HCl in ethanol (ethanolic leachate) at room temperature and with a liquid-to-solid ratio (L/S) of 10.

The caption:

Figure 4. X-ray diffractograms of the Greek BR (pristine BR) and the solid residues after leaching with 0.7 mol L–1HCl in water (BR after aqueous leaching) or 0.7 mol L–1HCl in ethanol (BR after ethanolic leaching). The dotted red lines emphasize the particular reflections of NaCl in the diffractograms.

The caption:

Figure 5. Breakthrough curves of BR leachates with (a) 0.7 mol L^(–1) HCl in water (aqueous leachate) or (b) 0.7 mol ^(–1) HCl in ethanol (ethanolic leachate) by 2 g of the SILP. The flow rate was 0.1 mL min^(–1).

The caption:

Figure 6. Recovery of elements by 2 g of the SILP from 1 mL of BR leachate with 0.7 mol L–1 HCl in water (aqueous leachate) followed by elution with 9 mL of 0.1 mol L–1 HCl in water, and from 1 mL of BR leachate with 0.7 mol L–1 HCl in ethanol (ethanolic leachate), followed by elution with 9 mL of ethanol.

The caption:

Figure 7. Chromatography separation of scandium (Sc) from (a) aqueous or (b) ethanolic BR leachates. Mobile phases: (A) 1 mL of leachate of BR followed by 9 mL of 0.1 mol L–1 HCl for aqueous leachate (a), or 9 mL of ethanol for ethanolic leachate (b); (B) 0.1 mol L–1 HCl; (C) 0.1 mol L–1 H3PO4; (D) 2 mol L–1 HCl. Flow rate of leachates was 0.1 mL min–1 and of eluents was 0.5 mL min–1. Dashed lines mark the volume of each mobile phase. Dotted lines mark the elution of iron (Fe).

Some more commentary from the text on metal separations:

Generally, iron separation from common minerals of the major base metals (e.g., Cu, Zn, Ni, and Co) is a major challenge in hydrometallurgy.(58) The present study in which iron(III) is separated from the BR leachate using ethanol and the SILP demonstrates the potential of solvometallurgical methods for tuning flowsheets for metal recovery. On the basis of environmental impact and toxicity, ethanol is generally considered as a green solvent.(59) It can be produced from biomass and is usually available in large quantities at a low price.(59,60) Therefore, apart from its performance ethanol is a sustainable solvent, which is the requirement for solvents used in solvometallugry...

Corn is physically green, of course, but I question whether corn ethanol is really "green," in the way many people take it. I do believe that it may be possible, with sufficient energy, to generate from carbon sources, including carbon dioxide, ethylene, from which ethanol can be conveniently made. Ethanol from corn may not be sustainable owing to the depletion of phosphate ores; we'll see.

The authors in any case continue:

...After scandium was separated by elution, the column was regenerated with 2 mol L–1 HCl (Figure 7). The column effluent after elution of the remaining components of the aqueous leachate of BR was mainly composed of a mixture of the major elements, namely iron, aluminum, and calcium (Figure 7a). Silicon and the majority of titanium were separated from other elements in the first fractions. The mixture of silicon and titanium can be used, for instance, in the synthesis of titanium silicate materials for catalysis and adsorptive separations.(61) By elution of the remaining components of the ethanolic leachate of BR (Figure 7b), titanium was collected in fractions together with aluminum and calcium. Their mixture can be considered as a potential precursor of a CaO–Al2O3–TiO2 slag for steel refining.(62) Moreover, their fractions were free from iron, as iron was eluted with ethanol in the initial fraction, along with silicon. The iron-silicate fraction could be considered as a resource for abrasives for blast cleaning. Another potential application is in the production of FeCl3, which is used for wastewater treatment and in the production of printed circuit boards.(63) Yttrium was eluted with 2 mol L–1 HCl along with the major components of both aqueous and ethanolic leachates. The separation of yttrium has not been performed since the focus of the present study falls on opportunities in solvometallurgy for scandium recovery. However, it has been shown by the previous studies that yttrium can be well separated by gradient elution of the SILP with phosphoric acid.(17)

The UV spectra may be out of context outside of the full text, but it bears on iron separations.

The caption:

Figure 8. UV–vis absorption spectra of BR leachates with 0.7 mol L–1 water (aqueous leachate, dashed blue line) or with 0.7 mol L–1 ethanol (ethanolic leachate, full green line).

The peak at 221 corresponds to the aquo/chloro complex of iron (III).

Excerpts from the conclusion:

Screening of the three sorbents (SiO2, SiO2–TMS–EDTA, and the SILP) for recovery of scandium from water, ethanol, isopropanol, ethylene glycol, and PEG-200 solutions revealed the potential of the SILP for scandium separation from the ethanolic leachate of BR. The BR was leached by 0.7 mol L–1 HCl in ethanol or in water. The leaching efficiencies of scandium and a vast majority of other elements were similar to both lixiviants. However, the sodium concentration in the ethanolic leachate was significantly lower compared to that in the aqueous leachate due to the limited solubility of sodium chloride in ethanol. Moreover, silica gel formation was suppressed by leaching with 0.7 mol L–1 HCl in ethanol, unlike when the leaching was performed with 0.7 mol L–1 HCl in water. In the breakthrough curve studies with the aqueous BR leachate, the uptake preference of the elements by the SILP was Si ? Ti < Na < Ca ? Fe ? Al < Sc < Y. The sequence was in part reversed when the uptake of the elements was performed from the ethanolic leachate, that is, Si < Fe ? Ti < Sc < Al < Y < Ca < Na. The reversal in trend was partly rationalized based on the change in solvation of the metal ions in the ethanolic leachate. Iron(III) was easily separated from the majority of other components of the BR by elution with ethanol in column chromatography with the SILP...

... About 84% of scandium was separated from other components of both leachates of the BR by elution with 0.1 mol L–1 H3PO4. Still, a high sample throughput and concentration of scandium from the ethanolic leachate by the SILP was not achieved. Apart of iron and silicon, other major components of the ethanolic BR leachate were recovered by the SILP along with scandium. Nevertheless, the study gives new insights on how a simple change in solvent in which metals are dissolved greatly affects the entire process for metal recovery...

What we are leaving for our children, our grandchildren, and indeed our grandchildren's great-great grandchildren is a huge pile of waste while we squander materials on fantasies like so called "renewable energy."

Be that as it may, we are leaving clues about how something might be done in even harsher times which are surely coming out of our indifference. This little paper is intriguing, I think.

Have a nice day tomorrow.

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