Results Back From Hayabusa2 Mission to Ryugu

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 is in Short Supply

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.

On the Slow Progression to Fascism

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.

Liquid Gallium-Platinum Catalyst

An interesting article has just come out on a liquid metal platinum/gallium solution catalyst composition showing substantially greater activity. The article reference is: Rahim, M.A., Tang, J., Christofferson, A.J. et al. Low-temperature liquid platinum catalyst. Nat. Chem. (2022). https://doi.org/10.1038/s41557-022-00965-6. The publisher charges for a download of the article. I didn’t shell out $32 for a copy so all I’ve seen is the abstract.

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.

Russian Media is Simmering About the War

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.

Some Pragmatics of Green Chemistry

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.

A Disgusting Spectacle

It’s striking how the police in Uvalde were intimidated into inaction by a teen-aged shooter armed with a controversial weapon used in the manner for which it was designed- the projection of overwhelming power and violence. While children in the classroom pleaded for help on 911, armed and trained police and terrified parents stood outside and waited while children and teachers inside each died a bloody, violent death. Their last moments of consciousness were saturated with blood, gore and terror.

In the follow up, the Texas Republican political apparatus has struggled to respond to the slaughter while being careful not to alienate their macho gun totin’ Texas cowboy conservative voters. Meanwhile, in Houston at the NRA convention, and while musical acts were fleeing from the event, the show must go on. The convention was an opportunity gladly taken by #45 to pontificate at length to core voters and amplify all of the worries he himself planted.

School shooters tend to be young males so perhaps there is a tendency to blame “toxic masculinity”. We cannot blame men for displaying at least some amount of masculinity. However, when we show it by strutting around like a peacock in an ostentatious display of weaponry and decked out in militia costumes, we are beaming a stark message to those around us to beware. Its intent is always to intimidate. It is an asymmetry in power- a necessary condition for many.

Nothing new is to be said here about gun rights vs gun control. Weapons culture and politics will have to evolve for a few generations before that can be reasonably addressed. Many more mass murder scenes will come and go before shoot ’em up cowboy masculinity fades away, if ever. In the near term, however, we can do something about our exposure to violent entertainment.

We Americans entertain ourselves with movies, television and videogames that feature gunplay as a plot device and an easy form of conflict resolution. We love to see the good guys hand out 9mm justice with righteous gunplay. American movie makers know full well the attraction of audiences to gunplay in a storyline. What better way is there for screenwriters to keep the energy going in a screenplay than to throw in scenes with shootouts. And how do characters gain absolute power over someone? They point a gun. Is it any wonder that now and then a few kids obtain easily available firearms and try shooting as a way to vent their rage and frustration? How do we learn to be adults? We mimic.

The entertainment industry needs to account for their part in the poisoning of our civilization with highly detailed dramatic portrayals of violence. The excuse that viewers have free will and should be able to discriminate between reality and fantasy is only partly valid. There can be no denying studio influence over impressionable young people. It is human nature to learn from and mimic what we see, even from film. The entertainment industry has normalized gun violence in the minds of our population. Behind the glitzy facade of show business is a deadly serious capitalistic enterprise that banks on whatever it takes to sell ads and tickets. And, if violence sells, they’ll crank out more of it. We need to quit buying so much violent content.

Chaos at the EPA

It’s difficult to describe how badly the New Chemicals division in the Office of Pollution Prevention and Toxics (OPPT) at EPA is performing these days, but let me try. The commercialization of new chemicals (not on the TSCA Inventory) not otherwise regulated requires that new chemical substances (NCS) be reviewed and granted following a Pre-Manufacture Notice (PMN) or a Low Volume Exemption (LVE) submission under the Toxic Substances Control Act (TSCA), should they meet internal criteria regarding safety. Exposures and doses to workers or the environment may be measured by the applicant or modeled using EPA in-house software. R&D only chemicals are exempt from such evaluation no matter the scale.

The application process requires the disclosure of the NCS composition and structure, the manufacturing and/or use operation in considerable detail, physicochemical properties and, if available, a wide range of worker and environmental hazards. Imported chemicals not on the TSCA inventory also require TSCA approval just as though they were being manufactured in the USA. Food, drugs and pesticides are not controlled under TSCA. Under penalty of law, all submissions must have the best and most accurate available information, particularly with regard to hazard information. No fibbing allowed.

The issues I’m about to recount started sometime in early 2021. Some speculate that a particular interpretation of the law promulgated by TSCA was adopted. I can’t provide references, however.

By statute, an LVE filing for instance, must be examined and be given a grant, conditional grant, or denial within 30 days. It is currently taking much longer than that: 60 to 100 days or longer. I have some that are still pending after 7 months. PMN filings take longer to process, about 9-12 months. or worse.

Aren’t these delays just a petty annoyance? Well, no. Part of a new product development timeline is getting regulatory approval. If this approval is subject to large delays with uncertain outcomes, then the launch date can become very fuzzy. The consequence for the end user is that scheduling their production activity becomes impossibly vague. Denials of LVE and PMN filings are not uncommon. Don’t expect a lot of sympathy from customers about EPA problems.

The last thing you want is some plebe right out of school with no professional experience in commerce to be handing out the regulatory death penalty to your expensive new technology. Handling hazardous materials safely and without environmental harm is done all day every day all over the world. There is a saying in the chemical industry: If you think safety is expensive try having an accident. There is considerable financial incentive to running a chemical plant safely and within regulations.

There seems to be a troubling issue involving the assumptions that EPA makes in regard to handling the NCS. The feedback I receive suggests that the engineers and toxicologists are ruling based on the worst case exposures that they imagine are going to happen. They imagine that workers and the environment will be exposed to the NCS as if workers aren’t wearing personal protection equipment (PPE) or there was no barrier to the environment. You can plainly state that these exposures won’t happen and state why, but they want evidence evidence that they cannot define that something will not happen. In other words, they want proof of a negative.

Another problem with EPA seems to be the sophomoric view that chemical hazards can always be abated by using safer chemicals. There may be a speck of truth to this generalization. In the formulations industry, for example. Replacing hazardous ingredients in mascara or shampoo with those that are less hazardous may be quite uncomplicated. Reducing chemical hazards is part of ethical business operations and is expected with ISO 9001 registration. The catch for chemical manufacturing is that the chemical features that make chemicals reactive and hazardous are usually the same features that make them essential to synthesis. Except for solvents and filter aid, unreactive chemicals are not very useful in synthesis. Synthetic chemistry is about manipulating the reactive features of one molecule with another to yield a useful product.

The delay issue is not unknown to EPA. In fact they are painfully aware of it all the way up to the EPA administrator. The good folks at EPA are doing their best with absurdly limited resources. We’re told that the TSCA division is 50 % understaffed, and many of the staff they do have are inexperienced. They have a computer system that is obsolete by many generations. You can see this by filing on their website. They have taken to denying submissions that are flawed in a minor way rather than continuing to work with the applicant to fix the problem. This excess fastidiousness ratchets down their backlog, at least in the short term.

The problems at EPA stem from the inability of congress to buckle down and provide proper funding. Only congress can act to boost staffing or computers. Lobbyists are working on it but, unfortunately, this is not an appealing issue for a congress person to take up and run with. Maybe we can get that cancerous A-hole Tucker Carlson to howl about it on the tube. Then we might see some movement.

Replacement Theory on Ice

I’ve been marveling at the current social phenomenon of “Replacement Theory” and all of the fear and loathing these words can generate. Anything that could plausibly rile up white folks is being scooped up and slung at the wall to see what sticks. The Republican fear machine needs and thrives on this kind of stuff. Fox News “Speaker to Animals” Tucker Carlson has been slopping it around the swill bucket lately as is customary for him to do. It’s become a meme with news coverage like a new Disney on Ice show.

Peering out from under my rock along the riverbank, it appears to me that there are a great many citizens in the U.S. of A. who enjoy nothing more than to get lathered up and vent their rage at the bogyman of the month. Some folks seem happiest and most alive when they are really hacked off.

I wonder how these folks will react when someone reminds them that social replacement is not new. After all, what happened in the forced removal of the Native Americans over the last 400 years? How many countries have we attempted to reconfigure to something more politically subservient by force or subterfuge? History is one long, highly blemished series of one people replacing another. Notice the irony? Historically, most change has been quite violent. Many nations have been complicit in the forced swapping of ethnic groups in the social and economic order in someone else’s land. It seems to be a natural turn of events.

If it is happening to the US right now, it seems to be relatively peaceful and quiet, except for the angry white nationalists out shooting people. More than a little change going on is merit-based selection in job placement and by the hard work of immigrants. If you are angry about being replaced by non-whites, first try not to murder people. Murder is the answer to a whole slew of poorly formed questions.

Oxy CEO on Oil Production

The CEO of Occidental Petroleum, Vicki Hollub, said an interesting thing last week as reported by Reuters. The article begins with a quote by Hollub.

“HOUSTON, May 11 (Reuters) – Oil companies worldwide have been trying to increase production, but are struggling to balance increases without undercutting shareholder returns, Occidental Petroleum (OXY.N) Chief Executive Officer Vicki Hollub said on Wednesday.” [Italics mine]

The effect on executive decision makers of “undercutting shareholder returns” is not to be underestimated. When margins are high, why voluntarily reduce them with increasing production?

She goes on to say-

“”It is almost value destruction if you try to accelerate anything now,” Hollub said during a conference call to discuss the company’s first quarter results.”

Everyone knows there is widespread public anger and distrust simmering on the matter of high gasoline prices in the US. Fuel prices are at a reported 14 year high and are helping to drive inflation. Everyone is feeling the pain either directly as a tank full of 85 octane or in the inflated price of widgets elsewhere.

Oil producers are feeling the heat but are reluctant to increase production. Hollub said “There are a lot of headwinds to increasing production worldwide,”

Unfortunately, the only market lever consumers have is to reduce fuel consumption.

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