Somebody set off a bomb at the Guidestones in Georgia causing serious damage to the monument. Georgia GOP primary candidate Kandiss Taylor had urged the destruction of the “Satanic Guidestones”. And somebody done went and did it. The writing on the Guidestones said-
“Maintain humanity under 500,000,000 in perpetual balance with nature; Guide reproduction wisely, improving fitness and diversity; Unite humanity with a living new language; Rule passion, faith, tradition, and all things with tempered reason; Protect people and nations with fair laws and just courts; Let all nations rule internally, resolving external disputes in a world court; Avoid petty laws and useless officials; Balance personal rights with social duties; Prize truth, beauty, love … seeking harmony with the infinite; Be not a cancer on earth — leave room for nature — leave room for nature.”
It’s pretty radical. Imagine promoting the idea of fair laws and just courts. Or seeking harmony. All without the mention of a deity and supernatural dominion. Obviously, this absence of religious underpinning automatically infers the foul deeds of Old Nick, the Prince of Darkness, or Mephistopheles. Mercy sakes alive! Planting a monument that offers secular suggestions of living a good life for its own sake. It was a scandal.
The only friction spot I can see is the suggestion of a maximum world population of 500 million. I think most biologists would agree with this, but it ain’t gonna happen. Imagine trying to suggest to folks to be smarter about reproduction. Overpopulation is happening and only famine, disease, or nuclear world war will slow it down.
There are easily enough folks around who indulge their Iron Age beliefs strongly enough to produce someone who could construct an effective bomb and use it. I’m sure somebody up in the holler was dancing a jig afterwards.
An interesting question and answer piece has come out signed by Mykhailo Zahorodnii, Ukrainska Pravda. Zhyttia, titled (by Yahoo) “The atrocities committed by the Russians are their reaction to the fact they are nobody in their own country“. It is not a dispassionate bit of analysis by a senior historian, but rather by an experienced reporter from Ukraine. Yes, it is anti-Russian. It does not attempt to convey sympathy or fairness towards the Russian people. But, as one-sided as it is, I think that many valuable insights are made into the consequences of Russian history and also its politics over the last 30 years.
“And it [the Russian army] is doing the same thing to Ukraine as to Syria. That is, it is technically possible to turn every Ukrainian city into Aleppo. There are orders, there is no honour, there is no dignity, there are no human values.”
If Ukraine is to lose the war, then Russia should be made to pay dearly for it. However, Putin has stated Russian nuclear doctrine- they will only use nuclear weapons if the survival of the state is threatened. This is widely held to be true. The big question is, who decides what the existential threat to the state looks like? Putin decides, of course. This is why the US and Europe must avoid a ham-fisted foreign policy with Russia. The Russian president is a belligerent madman in charge of a nuclear state and whose fantasies about Russian manifest destiny are his guide. Tensions with Russia are here to stay for many years. Putin supported Trump for a reason. Trump “respected” Putin for unknown reasons. We need to keep American madman and rogue narcissist Trump and his ilk far away from foreign policy.
The town of Uravan, Colorado, shows up on maps and road signs. You might think it is a physical town. It sits north of Naturita (pronounced natter reeta), CO, on Hwy 141 about 15 miles up the narrow San Miguel River valley. If you look at it’s Wikipedia page, you’ll see a picture of a bare area of ground. Today all that remains at the surface is a ball field and picnic tables. Every bit of the town and the mill has been demolished, shredded and buried within the confines of a Superfund site. Even contaminated bulldozer blades were buried on-site. Also remaining is a Umetco commercial building. Umetco, a Dow Chemical subsidiary, was responsible for managing the reclamation of the site which lasted from 1987 to 2007.
Main uranium deposits in the US (DoE Office of Legacy Management, 2015)
The local topography consists of sandstone canyons and mesas. The map below (north is up) shows a large area of land west of the valley mill site and up above on Club Mesa. This is the location of buried mill tailings and other contaminated materials. The major radiological contaminant is Radium-226 and its daughter products. Radium is a common and troublesome constituent in uranium-bearing ore.
As an aside, I would recommend taking Colorado Hwy 141 from Naturita north through Gateway enroute to Grand Junction if you’re in the area. Truthfully, Uravan isn’t along the route to somewhere most people would want to go except for locals. This stretch of road is called the Unaweep-Tabeguache Scenic Byway and is absolutely gorgeous. Just like in nearby Arches and Canyonlands National Parks, red sandstone is the dominant country rock in that part of the Colorado Plateau. You’ll drive through breathtaking canyons of red sandstone along the Dolores River, south of Gateway.
During its post-WWII heyday, the company town of Uravan, CO, was one of a number of thriving yellowcake boomtowns in Wyoming, Utah, Colorado, and New Mexico. Overall, there were over 900 uranium mines in operation. The name “Uravan” comes from the URAnium-VANadium ore that was processed there. Uravan was one cog in a large wheel of uranium production first for the Manhattan Project then for the Atomic Energy Commission..
Uravan produced concentrate which was was trucked to Grand Junction, CO, to the Climax Uranium Mill for further processing. Activity at the Climax site began in 1943 for uranium procurement and processing of vanadium mill tailings for uranium.
An excellent timeline of uranium history in western Colorado can be found at the Museums of Western Colorado web site.
The earliest mining activity at what became Uravan was for radium recovery beginning in 1912 and falling off by 1923. By 1935 the mill was expanded for vanadium recovery and from 1940 to 1984 the mill was used to process uranium and vanadium.
The predominant ore that was processed at Uravan was Carnotite with a nominal composition of K2(UO2)2(VO4)2·3H2O with variable waters of hydration. Elemental uranium is a dense silvery metal that oxidizes in air, reacts with water and dissolves in oxidizing acids. It has two important oxidation states: the +4 uranous oxidation state which is green and the +6 uranyl oxidation state, UO22+, which is yellow. The uranous form is found in the UO2 mineral Uraninite and the uranium silicate Coffinite. The uranyl vanadate form is found with potassium cation in Carnotite, with cesium in Margaritasite, and with calcium in Tyuyamunite.
Uranium-vanadium rich sandstone is found in Club Mesa to the west and just above the town of Uravan. This occurrance is part of the larger Uravan Mineral Belt which encompasses local commercial grade uranium ore. The mesa covers 6 sq miles and is bounded by the San Miguel River, the Dolores River, Saucer Basin and Hieroglyphic Canyon. According to the United States Geological Survey (USGS), the average grade of the ore ranged from 0.25 to1.5 % U3O8 and 1.5 to 5.0 % V2O5 (ref 1).
From an extensive drilling study by the USGS, the Salt Wash member of the Morrison formation sandstone of the late Jurassic age was found to be the host for most of the commercial-grade (in 1957) uranium-vanadium in the Club Mesa area.
Beginning in 1936, the mill site was owned by US Vanadium Corporation and built up to process vanadium ore. An entire town was constructed on site to accommodate workers. It also produced a uranium oxide side-stream as a yellow pigment. Then along came the nuclear age.
References
(1) Results of US Geological Survey Exploration for Uranium-Vanadium Deposits in the Club Mesa Area, Uravan District, Montrose County, Colorado, Boardman, Litsey, and Bowers, May, 1957, Trace Elements Memorandum Report 979.
So, it turns out that I did time in Texas- 22 months to be exact. As a postdoc in a large central Texas city with the initials S.A. The natives were friendly, if not a little obsessed with the daily level of the Edwards Aquafer. If you absolutely have to live in Texas, SA is a decent choice. I do have to fault them on their choice of US Rep. Louie Gomert. An actual gibbering dunce if there ever was one. Imagine what kind of people were passed over in making that choice? But I digress.
On to the point. The Texas State Board of Educators recently made the news regarding their decision NOT to replace the word “slavery” with “involuntary relocation”. Evidently this antiseptic language was floated by a curriculum study group. The board, to their credit, unanimously directed the work group to revisit the language. Astute choice, folks.
According to the article in the San Antonio Current, GOP lawmakers (are there any other kind in Tejas?) are trying to shield students from discomfort in the classroom as with the mercurial issue of Critical Race Theory. Previously, in 2015, headlines were made when it was discovered that enslaved Africans brought to the US by the slave trade were described as “workers” in a social studies textbook. Sanitizing language on slavery is the first step to eliminating its tragic history altogether.
A research article in the 9 June 2022 issue of Science reports analytical results from the samples returned from the Hayabusa2 mission to the asteroid Ryugu. Kudos to Science for making the article available for free. The craft rendezvoused with the asteroid 27 June 2018 and returned 2 samples with a successful landing in Australia on 6 December 2020. The authors report that they were allotted ~125 mg and used 95 mg of sample for the work in the article.
The article, by over 140 coauthors, is a densely written chemical/mineral/isotopic abundance paper for specialists in cosmochemistry (which is definitely not me). The article concludes that the samples resemble C1 Chondrites absent “sulfates, ferrihydrite, and interlayer water”. According to the article, C1 Chondrites bear a close resemblance in elemental composition to the solar photosphere.
Antimony, Sb, is an obscure metalloid that rarely gets much notice outside of a few highly specialized areas of technology. The element is most often found in the mineral Stibnite, Sb2S3. Antimony is a pnictogen found in Group 5 between arsenic and bismuth in the p-block of the periodic table. Crustal abundance is 0.2 to 0.5 ppm according to Wikipedia, making it several times more abundant than silver. It has many interesting properties and uses which will be left to the reader to discover. Interestingly, there is a rare allotrope of antimony that is explosive when scratched. Luckily, this is unusual.
In a May 6, 2021, article in Forbes, writer David Blackmon cites the many uses of antimony and where it occurs in greatest natural abundance. As it turns out, the US is not one of those locations where it is found in great abundance. China has the largest abundance of antimony- greater than half of the known reserves in the world, with Russia coming in second. At present, the US imports 100 % of this key strategic material. Blackmon writes-
“Antimony is a strategic critical mineral that is used in all manner of military applications, including the manufacture of armor piercing bullets, night vision goggles, infrared sensors, precision optics, laser sighting, explosive formulations, hardened lead for bullets and shrapnel, ammunition primers, tracer ammunition, nuclear weapons and production, tritium production, flares, military clothing, and communication equipment. It is the key element in the creation of tungsten steel and the hardening of lead bullets, two of its most crucial applications during WWII.“
According to Blackmon, China currently supplies 80 % of the world’s antimony and also imports ore from other nations for refining. Here is the kicker- China may soon run short of the element. Running short of antimony doesn’t just mean that prices will rise in short supply. It could also mean that China may stop exporting much of its refined antimony in favor of internal consumption to produce goods up the value chain. China tried to do this with rare earth elements already. A country rich in strategic minerals and a sophisticated manufacturing base is a country that can wield significant power over the rest of the world. In the US, antimony is considered critical to economic and national security.
The US has had only one mining district that produced significant antimony. That would be the Stibnite mine in the Stibnite Mining District near Yellow Pine, Idaho. Mining activity stopped in the mid-1990s. The district, like most of Idaho, sits atop the granite Idaho Batholith. Volcanic activity in the past forced hot water through cracks and fissures in the rock, dissolving soluble minerals, moving mineral rich hydrothermal fluids that, when cooled, precipitated as mineral veins in the granite. Antimony minerals are often associated with another Group 5 element, arsenic, in the form of minerals like realgar and orpiment.
The Stibnite mine began as a gold mine in 1938 during the Idaho gold rush. Throughout WWII, the stibnite mine produced 40 % of the antimony and tungsten needed by the US. Tungsten, or wolfram, appears as the tungstate salt with a metal cation like iron, calcium or manganese paired with a WO4 oxoanion. The hydrothermal fluid partitions minerals in a rock formation into concentrated zones through selective solubility. This process is responsible for the formation of veins in solid rock.
Oh look. I’ve driven off into the weeds again rambling on about minerals.
Caution. Political sentiment expressed below. Brittle folk may want to shuffle on by.
I’ve been trying and failing badly to keep my political thoughts out of this blog. I’m a left-of-center atheist white male scientist affiliated with neither political party. But things are happening in the USA. Bad things. I have come to believe they are indicators of a darker, non-democratic future. A slide away from democracy is a far too important a problem to leave to “others”.
For generations scientists have come to believe that the scientific establishment is and should remain a kind of a neutral cultural subset in the manner of Switzerland. But right now there are people aiming and succeeding to take power in the USA in order to dismantle and restructure what has been a fruitful civilization to satisfy their evangelical iron age religious urgings and their desire for some kind of ultraconservative Shangri-La where corporations rule and every teacher is a qualified sniper. While I exaggerate a little, progress is nonetheless being made.
Scientists can bring their quantitative analysis skills, their powers of persuasion and ability to find and use sources of credible information to the table. The ability to synthesize solutions to problems is another important skill that needs to be out and about. Scientists need to come out into the open a bit more.
A blog that I have long frequented but have never shared publicly is the Daily Kos. It is a popular progressive site consisting of staff writers and many guest contributors. Just as even I have to admit that occasionally a Republican writer has produced some valuable analysis and insight into things, I’ll propose the same about a progressive writer. That writer today is Thomas Hartman who is a progressive talk show host and NY Times best selling author. Recently he posted an article titled “What Would an American Fascist State Look Like?”.
I won’t waste time and bandwidth on a review of the piece, but briefly he articulates very clearly what it might look like to be in a state that is sliding into fascism and cites examples of common strong-man behavior. Now is not the time to begin to worry about a transition to a fascist state. The time to begin was 2016. We’re already behind.
As I stand here looking right then left, I see one political party that has made its intentions known regarding its determined path towards a Christo-fascist state. The other dithers and self-immolates into a dumpster fire with no strong leaders, lazy voters and ambitious ideals far too early for the present culture.
Being in chemical manufacturing, I can say that Platinum Group Metal (PGM) catalysts can represent a significant raw material cost in manufacturing even though it is used in “catalytic quantities”. Low catalyst loading is always desirable because of cost, but the trade-off is longer reaction time and/or higher pressure and temperature. Production scale high pressure vessels may not be available at organizations that do little high pressure work. At some point catalyst cost savings are canceled out by extended production time or more severe conditions. Fishing out catalyst from filter cake and preparing it for reuse can be time consuming and costly and may not be worthwhile.
Some PGM catalysts can even ignite a combustible atmosphere and also provide a dust hazard to workers. Extra handling is problematic. Most bulk suppliers take PGM waste back from their customers for recycle.
What has captured everyone’s attention about this gallium/platinum composition is the enhanced reaction rates reported for the electrochemical oxidation of methanol. Rahim et al. report a rate enhancement of “three orders of magnitude” over solid platinum catalysts at temperatures between 318 – 343 Kelvin.
The authors state that the Ga/Pt liquid catalyst mixture contains atomically dispersed Pt atoms within the gallium matrix. The mixture is prepared by simply contacting solid platinum pellets with liquid gallium to make a solution. Ideally, solid catalyst particles should be as small as possible to minimize the unfavorable surface to volume ratio. Solid platinum or other PGM catalysts are only active at the surface. The Pt/Ga mixture provides highly active atomic platinum at the liquid surface where presumably the chemistry happens.
In my experience with gallium, I’ve noticed that the metal will wet some surfaces like glass and plastic. Perhaps the gallium film on glass I saw is only an oxide layer- I don’t know. But it would seem that maximizing the availability of platinum atoms over a larger surface would be a good next step for even better efficiency.
If you want to see something unnerving, have a look at what Russian state television is broadcasting about their “special military operation” and NATO’s part in it. The have a “60 Minutes” program where a group of individuals offer their opinions on the war. In particular, the USA has been the target of considerable waspish criticism and open speculation on the best US targets for nuclear attack on the talk show. It is common for them to conclude that World War 3 has already begun and that they may as well get on with crushing NATO. According to presenter Olga Skabeeva, Poland could or should be next. Have a look and see what state-run media and control of the internet can do.
After following a chat room discussion on process safety, I find myself mixed on the matter of what is called green chemistry. In the present example, a fellow wanted to methylate a phenol but didn’t want to use dimethylsulfate or some similar methylating agent. He wanted something that was “green”.
Suggestions were varied, including a recommendation on the use of dimethyl carbonate as methylating agent and a few other approaches through aromatic substitution. One contributor wisely reminded contributors about going into the weeds with low atom efficiency.
“Green chemistry is the design of chemical products and processes that reduce or eliminate the use or generation of hazardous substances. Green chemistry applies across the life cycle of a chemical product, including its design, manufacture, use, and ultimate disposal. Green chemistry is also known as sustainable chemistry.” -EPA
When green organic chemistry is the goal in synthesis, it pays to be sure that there is an accepted definition of green chemistry on site. The merits and definitions are explained elsewhere. Difficult questions come up when a non-green substance is replaced with something that may be “more green” but needs 2 steps instead of 1. Or when green but more expensive reagents and solvents are needed. What is best? In this case, greater safety, lower cost, higher space yields, reduced waste generation, and fastest reaction times will be the real drivers. The business to business market will not pay more for a green product while a cheaper non-green alternative is present. If you want to get an existing customer to requalify an existing product from a new green process, be prepared to discount the price in exchange for the customer having to go through a requalification process. Customers do not like change at all.
Under what conditions would management allow a process choice that is greenish but obviously more costly? Possibly never. A greener process needs to give a cost savings somewhere. Barring draconian regulation, a successful green process will have a cost benefit. The benefit may be in lower direct cost of manufacture, satisfaction of a process requirement by a customer, or a hedge against future regulatory restrictions.
Solvents may be one of the easier opportunities for green chemistry. For a given process, there may be a bit of latitude with the solvent. Sometimes the issue of solvent residues in the product may arise. Some solvents are easier to strip away than others. No one will choose a green solvent that is hard to remove from the product. Again, the drivers will be those mentioned above.
Another green opportunity is when we automatically choose a stoichiometric reducing agent when we could have looked at a catalytic system with hydrogen. Catalyst costs per kilogram of product can range from negligible to high. One advantage of using expensive platinum group metal catalysts is that the metal is usually recyclable, which is greenish. However, any organic ligand present does get incinerated producing non-green emissions in the process of energy intensive metal refining. If catalytic hydrogenation requires the installation of new capital equipment, then the installation costs in time and money may prevent a switch.
For green oxidation, oxygen in the air is cheap and abundant but carries a big problem. Using an oxidizing gas in the presence of a flammable liquid reaction mass can give rise to an explosive atmosphere in the headspace of the reactor. This is a non-starter in industry. Catalytic oxidation using a greenish primary oxidant in solution is a good place to start. I’ve heard of hydrogen peroxide or peroxyacetic acid referred to as greenish.
The big problem with green synthetic organic chemistry is that in order to synthesize a molecule, the structural precursors must be sufficiently green, reactive and selective to run on a reasonable timescale and at acceptable cost. And they must not produce non-green side products or wastes that spoil the advantage of the target green step. A weighing of the pros and cons of any attempt to do green chemistry will always be needed and subjective decisions will be made on what constitutes green.
While we are all struggling to be greener, let’s not forget to remind ourselves and others that reduced consumption of almost everything is a green step we can all take right now.
Lamentations on Chemistry 