I have noticed that ChatGPT has been visiting this site more and more frequently. I can’t tell what posts they have been visiting. I do write the occasional humorous or lampoon style of post so I hope for the sake of mankind that ChatGPT can tell the difference.
We’ll see if my fictional Poltroon University gains wider recognition from AI.
It is amazing what you’ll find by just looking around. While reviewing recent blood test results it occurred to me that I didn’t know the first thing about albumin as a protein. A Google word search led to numerous links but provided many images as well. The crystal structure is below.
It is not uncommon to describe the enzyme-substrate complex as a highly specific lock and key structure. In the earlier literature is was axiomatic that enzymes are described as being highly substrate specific and use a single binding site for a given substrate. This notion is not always correct as the above graphic shows. Albumin is produced in the liver and is sort of a molecular ox cart- it can transport many substrates in the blood.
The job of human albumin is to get various substrates mobilized in the bloodstream and offer them at a desirable location. With the high molecular weight of enzymes, and the consequent low molarity available, it is astonishing that the heat of binding of substrate to enzyme can be measured at all.
One way to determine binding enthalpy and stoichiometry of a substrate to enzyme is ITC- Isothermal Titration Calorimetry. These calorimeters are available from several manufacturers such as TA Instruments and Malvern. ITC is just a type of reaction calorimeter that allows for immediate access to the reaction mixture. It is a microscale RC1 in effect. An enzyme solution can be titrated with substrate allowing for a visual determination of an equivalence point where 1 eq of enzyme active sights just matches the titrant equivalents. From such an experiment both enthalpy and stoichiometry can be measured. The image below is from TA Instruments and nicely shows the graphic output of an ITC experiment.
Above, the background signal from the buffer represents noise in the enthalpy signal.
TA Instruments also offer equipment for so-called nano scale experiments. See below.
The TA ITC specification table. Note the minimum heat in the low volume column: 0.04 to 0.05 microJoules with a 190-microliter sample cell size.
Albumin is endowed with binding sites open to a variety of substrates. It is like a wheelbarrow or an ox cart. It can ‘carry’ numerous substrates across several categories.
The downside of such low specificity is that albumin can bind many drug compounds at the expense of dose delivery to the desired site. Doses of drugs must be adjusted to account for drug lost to blood proteins like albumin.
Some folks have all the luck. America’s Orange Jesus has been (or will be) offered a Boeing 747 to use in place of the two presidential B747s which had developed an annoying rattle and had to be taken out of service. They are presently parked at Oskar’s Jet Shop and Grill somewhere in the Pacific Northwest. In sympathy to this niggling inconvenience to #47, an old man, the royal family of Qatar has generously stepped forward and offered a super luxury B747 for the Great One for his weekly trips to his many resorts. The B747 will transfer to #47’s Presidential Library foundation where it will remain. Some are saying that it will cost a gigabuck to upgrade it as necessary.
Keeping a third B747 ready to fly at any given moment will be expensive as are the 2 presidential jets now in the shop. In the new B747, the lavatories will have to be reduced in size for the media’s discomfort. Vending machines will be added for feeding the media but will be limited to exact change only. The machines will also offer #47’s trading cards which will include a 5 % discount coupon for his golden sneakers. As always, payment can be made with #47’s cryptocurrency plus a $50 service charge.
As the authoritarian regime of #47 continues to take hold, an increasing number of governments will express fealty and line up to offer something special, which #47 will gladly take and keep, the emoluments clause notwithstanding, found in Article I, Section 9, Clause 8 of the U.S. Constitution. It has already begun to turn stomachs worldwide but others will be attracted to the new ‘democratic dictatorship’ ramrodded by the GOP and led by the Orange Jesus himself. Many people around the world tolerate authoritarian leaders or see them as admirable strongmen. Kick ass and take names, some say. But too often the names aren’t taken or made available to anyone. There is just the ass kicking and transfer to a holding facility. Habeas Corpus? Gone! Evidence of a crime? Nah. Filing an appeal? What, are you being serious?
To the many readers outside the USA, know that a very large number of US citizens are horrified and in serious opposition to #47 and his MAGA movement. However, it seems that the Founders of this country failed to anticipate a situation where a single party rules both houses of Congress, the White House, the Supreme Court, and the governors and legislative bodies of many states. The Founders assumed that the checks and balances between the three co-equal branches of government and built into the government they designed would protect the democratic republic and keep essential government services working. They could not anticipate a simmering populist movement amplified by instantaneous social media. Whereas in times before the internet and smart phones, a large number of disaffected and under-educated citizens in America now have access to media of all kinds and can gravitate towards whatever populism that appeals to them. There seems to be little in the way of concern about truthfulness.
The single party dominance of MAGA in US government means that enforcement of federal laws or procedure will be ignored. The Department of Justice has been slow to enforce checks and balances or just ignore it altogether. MAGA GOP politicians know that endorsement by #47 ensures that they will get votes from MAGA block and assure their political careers.
Roughly 30 % of the voting population will support #47 until their dying day, regardless of his behavior. Resistant to the lessons of history and logic, they are essentially lost to modern times. They are angry from seeing and hearing the hype surrounding modernity and the corrosive conspiracy theories involved. Not having a college education, they missed out on opportunities that open up by living in a college environment. All of the job descriptions and opportunities requiring college education aren’t necessarily posted off-campus and are therefore missed.
Until I entered the university, I was completely unaware of a host of career choices available. I grew up in a rural midwestern blue collar environment and was completely unaware of the various futures available. Many have glorified our rural culture, but I found it quite boring in my years from birth to 14 years. Sure, there are wide open spaces and nature. But the fifth time you wander out into a large pasture you begin to realize that solitude is nice but quite boring.
I was introduced to science and technology by watching the progress of the Apollo moon mission in the 1960s. It was thrilling but there was no one around who could hold a decent conversation about it with me. Basically, if you were a kid into science at that time in my state, you were alone. Just knowing about sciency topics wasn’t enough. It is nice and necessary to have discussions to explore ideas and ask better questions. To share in the wonder and majesty of the universe. That’s not too much to ask, isn’t it?
It has been revealed that the time to the demise of the universe by decay has been lowered substantially from 101100 years to 1078 years.
Wow.
This changes everything. I’ve always wanted to try oil painting, so I best get started.
Many countries including the US have underground strategic gas & oil reserves. At present the US has 4 salt dome petroleum storage sites in Texas and Louisiana along the Gulf coast. Salt domes are convenient and inexpensive for underground storage of crude oil and gas. Salt mining has been done from underground workings of drifts and shafts employing underground miners. It has also been accomplished by hot water injection into the formation and retrieval of NaCl brine. Sometimes the salt dome is capped with a layer of elemental sulfur which is recoverable.
The dome formations, called ‘diapirs‘, are usually 1/2 to 5 miles across and rise to 500 ft to 6000 ft below the surface. The discovery of these salt formations coincides with the discovery of oil at Spindletop Hill near Beaumont, TX, in 1900. The current inventory in the SPR as of March 29, 2024, is 363.6 million barrels.
The US acquired the sites in 1977 after the 1973 oil crisis hoping to buffer large disturbances in the crude oil supply. In October of 1973, the Organization of Arab Petroleum Exporting Countries (AOPEC or OPEC) embargoed any country that supported Israel in the 4th Arab-Israeli War. The US was embargoed after Richard Nixon requested 2.2 $ billion for support of Israel’s war effort. At about the same time, after the US had disconnected the dollar from gold, OPEC Ministers found that with the free-floating dollar, their income was lagging because they did not have institutional mechanisms to raise prices with fluctuations in the market price.
Oil storage is all very interesting but what’s the deal with salt domes themselves? What do they look like and where are they found? Why do they form domes?
The graphic above is from a 1984 Atlas of Salt Domes produced at UT Austin. It shows the intrusive nature of an idealized salt dome. Salt strata are able to deform upwards due to the weight of the formation on the lower density and lower strength salt (halite) layer. The term “salt tectonics” has been used.
The collision of supercontinents Laurentia and Gondwana lead to compressional folding of strata and the formation of anticlines and synclines in the areas now lying in eastern Utah and western Colorado.
There are several types of diapirs: Magma, Salt and Mud. Salt diapirs start out as layers of salt sediment deposited. Here ‘salt’ refers to a number of ionic solids previously precipitated from an inland ocean. Changing sea levels and evaporation of shallow marine waters lead to the deposition of dissolved and suspended solids forming shales, dolomite, anhydrite, sodium and potassium salts, and black shale.
These salt strata do not consist purely of halite, NaCl, but rather contain other evaporites like hydrated gypsum, CaSO4 .2 H2O, and anhydrous gypsum or anhydrite, CaSO4. naturally, there may be layers of silt or sandstone included in the salt formation. If the salt strata form an anticline, oil, gas and water (or brine) may accumulate in the diapir.
Salt is less dense, has greater ductility and is more buoyant than the surrounding country rock. Under great pressure from the surrounding rock, salt can begin ductile flow in the direction of lower pressure which may be upwards. The salt formation has greater ductility than the surrounding rock, so the salt is extruded into faults and sediment layers above. This has been called ‘salt tectonics’.
Salt diapirs are more common than most of us realize. On the Gulf Coast they are found on both sides of the coastline and further inland. Sometimes they are associated with oil and gas deposits. Salt strata are found in Utah below Arches National Park and further south in the Moab valley and southeast into the Paradox Valley in western Colorado. The salt strata can be thousands of feet thick originating from marine transgressions of the Jurassic Sundance Sea. This is not to be confused with the later Cretaceous Western Interior Seaway.
The Sundance Sea moved in and out 5 times with a hiatus of erosion between transgressions.
At Arches National Park, over time the ground beneath the area had been rising, fracturing the sandstone above and producing the fin formations at the surface. The exposed rock, called the Entrada sandstone, is part of the Pennsylvanian Paradox Formation. The fins are comprised of many layers of sandstone. If the broad face of the sandstone fins erode enough, a hole can be formed giving the namesake arches. An aerial photograph shows parallel fin formations over a wide area.
If the reader has never explored Utah, by all means do so. It’s just gorgeous.
If you look the chart of elemental abundances in the cosmos below, you’ll notice that beyond hydrogen and helium atomic numbers, there is a steep log-scale drop in the abundances of lithium, beryllium and boron, or just ‘LiBeB’. This is followed immediately by a sharp exponential rise in the abundance of carbon, nitrogen and oxygen, etc. Beyond oxygen there is a general downward trend in elemental abundances. Well, except for iron, Fe. It is a special case related to the demise of stars. The zig-zag in the curve is explained by the Oddo-Harkins rule which postulates that even numbered atomic numbers are more abundant. I’ll leave this to the reader to explore.
Maybe 15 years back I decided to understand why each of the LiBeB elements are so scarce. And, if they are so bloody scarce, then how do they end up concentrated in ore bodies on earth? As a first-order approximation, you’d think that the explosion of stars and the resulting rapid dispersal of matter into the surrounding space would argue against the LiBeB concentrations on a planetary body like earth.
So, here is the question: Given that the cosmic abundances of lithium, beryllium and boron (LiBeB) are dramatically smaller than the succeeding light elements, how is it that “concentrated” ore bodies containing these elements exist on Earth?
As I look at it now, the answer is bloody obvious. But when I asked the question 15 years ago, my understanding of hydrothermal activity and fluid movement through the earth’s crust was pretty slim nonexistent. But hey, my focus in college was not astronomy or geology.
The graphic below shows how elements can be grouped according to a few particular categories. It is an absolute tragedy that the Platinum Group Metals (yellow shading) are in such the low abundance. These elements are uniquely valuable in chemical and industrial applications.
An even more fundamental question is, how is it that the cosmic abundances of lithium, beryllium, and boron are so low? Answer: they can’t survive the temperature and pressure conditions in the core of a star. They are fuels and therefore too delicate.
So LiBeB nuclei are produced during cataclysmic stellar explosions by some kind of spallation process, scattering fragments of larger nuclei into space. Another theory claims that cosmic radiation is responsible for the spallation of larger nuclei leading to LiBeB fragments. Subsequent generations of star formation resulting from an accumulation of hydrogen, helium, and heavier elements can lead to a star system with a protoplanetary disc where mass is brought into closer proximity. Mutual gravitational attraction between dust, chunks and aggregations of solid phase matter not already drawn into the star begin over time to aggregate and form planetary bodies. Some of the larger bodies are heated to liquid phase by collisions. Smaller mass objects may remain in the solid phase. Planet or moon sized bodies can collide to produce another planetary body or just debris. A fluid body of sufficient mass will spontaneously alter its shape in the direction of spherical such that all of the mass is as close to the center of gravity as possible. A spherical planet is one in which all of the mass is as close to the center of gravity with minimum potential energy as possible. A flat, disk-shaped body does not. It is hard to say just exactly how a flat planet-sized body would form with only gravity to drive it.
A cooling but still partially molten planetary body will begin to sort its large-scale composition by density and melting point. High melting point materials near a cooler surface will form solid crystalline bodies within the magma and then settle and possibly stratify according to density, then re-melt and disperse and convect to repeat the process. With cooling, the magma becomes increasingly viscous which would be expected to slow down mixing within the magma body. Over a long period, the planetary surface will continue to cool by loss of radiant energy and eventually the surface will crust over. Planetary bodies will accumulate mass by gravitational attraction as they sweep through space in their orbits, adding whatever chemical diversity that may be falling inwards to the surface. It seems reasonable to suppose that infalling dusts, rocks and asteroids are not uniform in their total compositions and may result in a non-uniform, spotty distribution of elements on the planet.
Solidification
Well before the surface cools to the point where a gas such as water can condense to form bodies of liquid water, water vapor in the atmosphere can convect to produce clouds at altitude, releasing latent heat and further adding to the heat transfer from the planet. Eventually, liquid water on the surface of a cooling planet can carry heat energy upward by conduction from the surface and atmospheric convection upwards, releasing the latent heat of condensation as clouds form in the upper atmosphere where it is colder. Heat transferred to the atmosphere will radiate infrared energy in all directions including space. The planet has developed weather.
Solidification processes in a magma begin to spontaneously partition or nucleate into particular combinations of elements. Some groups elements like silicates combine with metals into molecules (covalent bonds and ion pairs). For a period of time on any given crystalline surface, the temperature will support equilibration to and from the magma wherein ionic species will attach to the crystalline surface from the magma. With sufficient temperature, ions can detach from the surface and diffuse into the magma. This process will continue as the temperature drops freezing the magma and suppressing diffusion.
Bowen’s Reaction Series summarizes trends in the order of melting/freezing of various classes of minerals with temperature in magma. From location to location, the composition of magma is variable where some may be silicate rich and others silicate poor. That melting/freezing points of minerals vary with composition shouldn’t surprise my chemist friends.
Reaction selectivity is driven by the sign and magnitude of Gibbs energy in a particular transformation and the ability of the combination process to be reversed at the local temperature. The formation of crystals or their dissolution in hydrothermal fluids or magma is taken to be a type of reaction. Many of the species present at magma temperatures will be ion pairs.
A few covalent species like the highly stable Si-O bonds in silicates are found in great abundance. The O of Si-O may or may not be connected to other silicon atoms such as … -O-Si-O-Si-O-Si-O-Si-O- … for examples. There is no upper limit to the number of O-Si groups possible in minerals, though their assembly can go many directions. Quartz is a 3-dimensional network homopolymer. All 4 of the oxygens on silicon are connected to adjacent silicon atoms via the oxygen linkages. Quartz is a mineral comprised of all covalent bonds. Quartz has a much higher softening temperature than manufactured glass.
Silicon readily forms tetrahedral connections with oxygen as in silicate (SiO4)4- units. Si-Si bonds are not found in nature.
In a hydrothermal fluid solution or in magma, ionic species randomly diffuse, collide or swap partners. Charged species like iron (2+) cations can collide but will bounce apart owing to their like positive charges. But at a sufficiently low temperature, a sulfide (2-) anion can collide with the oppositely charged iron (2+) cation and remain connected as iron sulfide. The two ions are now chemically bonded and in doing so, heat is released and dispersed into the surroundings leading to a localized increase in temperature. Heat spontaneously flows from high temperature material to lower temperature material. The localized heated surrounding crystallizing minerals can keep dispersing the energy outwards, but as it encounters more mass which also absorbs heat energy, the resulting temperature rise diminishes rapidly as the energy is diluted over more mass.
Chemical transformations have two broad drivers- kinetic and thermodynamic. Kinetically driven transformations favor the pathways that are the fastest Thermodynamic transformations are equilibrium-controlled meaning that transformations that are reversable will favor the end state having the lower Gibbs energy. The Gibbs energy (ΔG) combines the heat of reaction (enthalpy, H) minus the entropy (S) times the absolute temperature (T). The entropy accounts for whatever heat energy may be gained/lost from/to the environment. When a bond forming reaction occurs, heat is released and moves into the environment.
Mineral nucleation starts with a microscopic “seed crystal or compatible surface” that will provide a template to further crystal growth by like molecules. Some combinations of elements will begin to polymerize forming high melting point, low solubility molecules comprising silicates and aluminates.
The concentration of the Li or Be or B into what would later become economic ore bodies is driven by the flow of ground water. Subsurface hot water flow in the crust is referred to as hydrothermal flow and from it is where concentration of the LiBeB begins. An ore body is a mass or formation of rock that is enriched in some particular element or group of elements. Usually, these elements are part of chemical compounds rather than pure elements. Gold would be an exception.
Definition- Minerals and Rocks
Mineral– A solid substance with a well-defined chemical composition and characteristic crystal structure.
Rock– A solid, naturally occurring aggregation of minerals.
Water, and especially hot water under pressure, will chemically alter the rock it is in contact with. While it is in contact, some fraction of the altered rock will dissolve and some components may be entrained as suspended solids in the fluid. This will extract and partition part of the altered rock into a solution with a range of possible compositions depending on solubility, pH, temperature and pressure. In this way, elements get partitioned into solution phase and away from the solid phase.
Hydrothermal solutions can sit in place for a very long time, eventually saturating with mineral components. If there is cooling in place, the saturated solution can precipitate to form a solid body of mineral filling the local spaces. The deeper the fluid, the warmer it will be and likely the slower it will cool. However, if the surrounding rock is porous or develops fractures or faults, the hydrothermal fluid will flow to the zone of lower pressure. If the flow is into a cooler zone, there may be precipitation of the least soluble components leading to solid mineral formation. Precipitation can also occur from a drop in pressure.
Solubility vs Temperature vs Pressure Example with Quartz
The effect of temperature and pressure on precipitation of silicate can be seen with the beautiful pressure/temperature/solubility relationship shown below. For instance, we can see that for temperatures at or below 150 oC, there is very little change in solubility of silicate with increasing pressure. On the higher side of the temperature scale at 350 oC, we see that there is a considerable solubility change with increasing pressure. At high pressure, say 700 MPa, the solubility of silicate is most sensitive to changing temperature.
The research article above cites the solubility of SiO2 in mg/kg water, or ppm. I am using the term silicate indicating hydrated and charged SiO2, the SiO4 tetrahedral form, which is known to dissolve in water. It is common in some of the geological literature to refer to the neutral oxide form of a mineral or metal.
SiO2 is often observed in its amorphous or crystalline topological polymer (or network polymer) form as a quartz vein, pegmatite or crystalline mineral component of a felsic igneous rock. Quartz found in a vein is there because a fault or fracture was available for filling with a hydrothermal fluid. As the curve above infers, saturation and precipitation can be abrupt with a sudden drop in pressure during a fault movement or sudden opening of a fracture network. Quartz veins are often accompanied by metallic gold in the upper oxidized zones (gossan) of the formation. In the context of mining, these veins are sometimes called quartz reefs.
Back to LiBeB
Although LiBeB elements are scarce, there are hydrothermal processes in the crust that can concentrate them in economic quantities.
An excursion into ore geology shows that selective hydrothermal extraction and transport are critical to the formation of a great many types of ore bodies. In fact, all three elements of LiBeB are moved by hydrothermal fluid transport on Earth at some point.
Lithium
Lithium metal is quite reactive and not found on Earth in the neutral metallic state. It is a single-electron donating Group 1 element and the lightest atomic weight metal of all the elements. Lithium has a large standard reduction potential of -3.05 Volts and is an excellent donor of electrons and a poor acceptor of electrons.
Lithium metal reacts with three major components of air: water, to form LiOH + H2; Oxygen to form Li2O + Li2O2 + H2; and nitrogen gas to form NLi3, lithium nitride. While other air-reactive metals can be stored under a hydrocarbon like kerosene for protection, lithium will float in these liquids and may be mixed with a heavy hydrocarbon or grease to keep it covered.
Lithium deposits can be split into two general domains- brines/muds/leachates, and hard rock deposits. Spodumene is the common hard rock source of lithium found in a few places around the world. Spodumene is lithium aluminum inosilicate and has a few variants such as Hiddenite, Kunzite, and Triphane coming from trace elements present in the surrounding rock.
The Silicate Zoo section is a bonus feature and may be skipped.
Bonus: A Step into the Zoo of Silicates
Spodumene is an inosilicate. Silicates as a group make up 90 % of the Earth’s crust. The basic unit is the tetrahedral [SiO4]4- silicate with 4 oxygen corners of the tetrahedron. These are known as ortho- or nesosilicates. The 4 minus charges are balanced by 4 plus charges provided by one or several metal cations at a time. Orthosilicates are the simplest variants of silicates.
The corner oxygen ions of silicate can be attached to the silicon of another silicate. These are called the sorosilicates and have the formula [Si2O7]6−.
Silicate units can also form rings called cyclosilicates. The rings consist of silicate tetrahedrons with alternating linkages of silicon-oxygen atoms. The general formula is [SinO3n]2n−.
There are several varieties of inosilicates. As a group they link silicate units into interlocking chains. There can be a single chain (pyroxenes such as spodumene) or two (amphiboles such as asbestos). The single chain inosilicates have the formula [SinO3n]2n−. The double chain inosilicates have the formula [Si4nO11n]6n−.
Phyllosilicates are sheet structures of silicate and have the general formula [Si2nO5n]2n−. This group includes micas and clays.
The tectosilicates are 3-dimensional frameworks and have the general formula [AlxSiyO(2x+2y)]x−. Note that aluminum may be present. This tectosilicate group includes quartz, feldspars and zeolites.
If you look at all of the general formulas, note that the negative charges must be balanced with positive ions (cations) of some kind. They are typically metal cations that vary in positive charge and ionic radius, although they can be capped off with hydrogen. A metal cation with its positive charge and ionic radius can be most easily replaced by a different metal with the same charge and similar ionic radius. Different charges and ionic radii are possible replacements but cause distortions in the lattice structure.
Minerals can form such that a silicate [SiO4]4- unit can be replaced by one or more aluminate (AlO4)-4 units and the metal counterions can be substituted by other metals of the same charge and similar ionic radius.
Back to Lithium
A growing fraction of lithium exploration and production involves lithium brines. Subsurface brines enriched in lithium (up to 0.14 %) can be pumped to the surface and exposed to sunlight in large evaporation ponds. Brines are saline solutions comprised of numerous soluble ionic substances. The lithium component must be isolated to a specified level of purity prior to sale. The most common product leaving a lithium mining operation is the insoluble lithium carbonate.
The process of concentrating a mineral from the ore is called beneficiation. An ore is comprised of the target mineral and gangue or mine waste from previous activity. The idea is to use economical physical and chemical methods to remove the gangue from the target mineral.
The largest collection of lithium brine reservoirs, known as salars, is in the Lithium Triangle in Latin America. The countries in the Triangle are Chili, Bolivia and Argentina. This area holds more than 75 % of the world’s lithium resources under their salt flats.
The salar brine is pumped into an evaporation pond and allowed to concentrate in the sunlight for a year +/-, then it is filtered and sent to another evaporation pond for further concentration. What happens next depends on which of the several possible processes is being used. The type of processing that is used depends on few things: The composition of the ore and interfering substances present; the company may have in-house technology they can adapt; there may be patent constraints in force; the process economics will apply considerable effects on equipment size and required annual throughput.
Economic ore is that resource which can be beneficiated and further refined and sold at a profit. So, the amount of ore that constitutes an economic deposit can shrink or grow with the market price of the product.
A recent development in lithium resources is the Rhyolite Ridge Lithium-Boron Mining Project near the ghost town of Rhyolite, Nevada, and southwest of Tonopah. The mine will be a large scale open pit operation operated by the Australian mining company ioneer. The mining will be carried out in the conventional drill-and-blast, and load-and-haul method. In the beginning the mining fleet will use automated haul trucks.
Even though nature has provided a concentrated lithium ore body, people still have to go to considerable lengths to produce economical lithium product, all the while gambling on the market price in the future.
Beryllium
Beryllium, Be, atomic number 4, has some very useful properties that make it a valuable metal. It is also quite scarce. The world’s richest beryllium deposit is located near Spor Mountain in Utah. The mine is operated by Materion Brush Inc., formerly known as Brush Wellman. The mine is operated by Materion Inc., formerly known as Brush Wellman. The beryllium rich tuff is located by trenching and drilling. Tuff is compacted volcanic ash that has been cemented into porous rock by contact with water flows. The area also contains fluorspar and uranium, separately, in combination with beryllium. Bertrandite (Be4Si2O7(OH)2) and beryl (Be3Al2Si6O18) are the chief beryllium-bearing minerals and fluorspar is a common accessory mineral.
Spor Mountain is located in South Western Utah in basin & range country that extends across Nevada to California.
The above map is from the US Geological Survey and shows 3 extinct calderas in the immediate Spor Mountain vicinity represented in blue. It is interesting that tuff, made from pyroclastic flows and ash where particulates are later cemented together, is the rock in which beryllium is found in the area AND there are 3- count ’em 3 -calderas right nearby. Coincidence?
Beryllium is a rare element on earth showing up in veins, pegmatites and tuff. In the cosmos its existence is thought to be due to cosmic ray spallation.
“The beryllium tuff is a favorable host for beryllium ore because 1) it is adjacent to faults and rhyolite vents where mineralizing fluids could enter the tuff, 2) it is a porous, reactive conduit for mineralizing fluids, including both hydrothermal and ground waters, and 3) it contains carbonate clasts, which reacted with fluorine-rich fluids to precipitate fluorite and beryllium.” Source: USGS, 1998
Boron
We’ll defer to the Wikipedia to provide background information on the element boron. The main source of economic boron is borax. Borax is a type of evaporite originating from hydrothermal fluids that have flowed to the surface where subsequently the water carrier evaporated to afford dissolved and suspended solid borax, a hydrated borate. Boron the pure element is not found, it only appears as set of various borates. There are monoborates, nesoborates, inoborates, phylloborates and tektoborates. The prefixes below are applicable to silicates and other oxides as well. The older Nickel-Strunz categorization system has been used to describe the classification of complex borate anions found in minerals.
The structures of borax and hydrated borax above have been reduced to their minimum hydration. In reality these are idealized structures not reflecting the agglomeration into larger hydrogen bonded structures. Neutral sp2 boron atoms have an empty, low-lying p-orbital which can bond to the O of O-H groups whether from water or other borates.
The actual composition of any oxy-borate including borax will depend on its thermal history and its chemical environment. Attempting to dehydrate a borate may indeed remove water, but in doing so may open up a p-orbital on boron that would allow an exchange of oxygen species, whether another borate, boric acid or just another water molecule. This is not worrisome when producing boric acid, but when one of the OH groups of boric acid is replaced with a carbon atom, then dimerization and trimerization may occur even at low temperature under vacuum to form boronic anhydrides.
When ordering an organoboronic acid, look at the specs very carefully. Sometimes the water spec may be quite broad due to adventitious dehydration. Using azeotropic removal of water will work by toluene azeotropic distillation, but you may not recognize the 1H-NMR spectrum of the toluene solution because this dehydration method may produce the dimers, trimers and oligomers from the original organoborate. In my experience, the anhydrides work very well in the Suzuki coupling.
A trial sample of an organoborate must represent what can actually be made at scale. A lab sample will have an analysis of what a skilled chemist can do under optimal conditions. If the customer wants bulk boronic acid matching the qualifying lab sample, then you may be sunk if you cannot reproduce the sample specs in the plant. Been der, done dat.
When submitting an organoboronic acid to a customer for approval, avoid sending the very best material from the R&D lab. They will spec on that sample and expect to see the same thing from a production run.
In the organic synthesis area that I have been witness to, boron showed up in our lives mostly for purposes of aryl coupling chemistry with an aryl halide, an organoboronic ester and a palladium catalyst. The nomenclature gets confusing with boron species. Borax is a borate because of the B-O-B and B-OH bonds. But KBF4, potassium tetrafluoroborate, has a boron-based anion with 4 fluorides. The -ate suffix does not always mean that oxygen is in the formula. Many anionic boron species have a net negative charge because a group like OH or F brought the negative charge to make a tetrahedral boron. Quaternary borates are often used as a weakly coordinating conjugate anions where non-interference by the anion is needed.
Lithium, beryllium and boron are all three transported by meteoric and hydrothermal water flows. When hot, pressurized water penetrates a fault or fracture system, the fluid can interact with whatever rock it is in contact with. Over long periods of time the fluid can corrode the wall minerals of the fault.
In this scenario, water can do several things to the rock. At the atomic level, the outermost layers of a crystal lattice in the mineral may be subject to aqueous hydrolysis making metal hydroxides, MOH, and liberating the anionic X– species from the latticework. Or, the water may just pull unaltered polar species into solution where they can swap ionic partners and either remain in solution or precipitate onto the surface features of the rock. If the hydrothermal fluids are in motion upwards to cooler regions above, precipitation may occur as the fluid naturally cools and depressurizing. Over time, layers of different insoluble material can stack onto the previous layers. This can go on until the void in the rock is filled and can no longer pass fluids through the fractured formation.
Conclusion
Despite the cosmic scarcity of each of the LiBeB elements, these elements may be found on or near the surface of the Earth concentrated as minerals in an ore body. Transport and placement of enriched individual LiBeB ores derives from multiple instances of differential solubility from the source rock to the ore body. Minerals that have more water solubility than adjacent minerals will tend to be transported in aqueous flows. The transported mineral gets concentrated in this way, but so do the minerals left behind. Aqueous flows at the surface can drop out their dissolved minerals as the surface water evaporates. As the surface water concentrates and cools, a sorting process is underway driven by solubility properties.
The original salt ion pair, M+X–, may be extracted into in water and dissociated to produce M+ and X– ions in solution. Other ionic substances like N+ and Y– can switch partners in a double displacement reaction and produce MY and NX. If it turns out that NX has poorer solubility than MY, then the mixture of M+X– and N+Y– will produce a precipitate of NX, leaving much or most of M+Y– in the water. Minerals deposited from evaporation are called evaporites.
Which is more desirable from the manufacturing perspective, the precipitate or the concentrated solution? Not being a mining engineer or an economic geologist, I can only speak as a person from the fine chemical industry. The precipitation of the desired product from a complex mixture seems a bit more desirable in that it is both an isolation and purification process. Often the solids can be washed and dried in a filter dryer and bang, you have your product.
Precipitating out an undesired solid component from a mixture, pure or not, while leaving the desired product in solution with solvent and other side components from the reaction is a bit less desirable. This version is at least another step away. If the product is a solid, perhaps a scheme can be found for precipitating it as well.
Notice: As an organic chemist and not a geochemist I will be using descriptions and vocabulary that may not ordinarily be used in geology. While a geochemist might easily write a lovely article that could bring tears to the eyes of the most sour geochemist, I will stumble forward with just my trailer park chemistry background- organometallic, organic, inorganic, physical and quantum chemistry.
When you step back and view mining technology as a whole, it becomes apparent that two of the largest scale inputs in mineral refining are water and electrical energy. On Earth diesel is also required in large quantities.
A good question for those who propose mining asteroids is this: Have you solved the water and electric power requirements for unit operations? Let’s say it is solved for one mineral. How will the value be mined, transported and gently lowered to the Earth’s surface without breaking into flaming pieces on re-entry or forming a crater in a city? Is there an element or mineral that is so valuable as to justify the costs and risks to be met for a space mining mission? Is it rhodium? Gold? Diamonds? Or what?
Do the people behind the fanciful images and hype believe that they only have to dock with the asteroid and grab valuable minerals from the surface? There is a good chance that the target ore will need exploration, excavation, and possibly some kind of blasting. The target elements may well be dispersed within the host rock. This will require comminution in preparation for further processing. The ore will likely need ore dressing which is the job of removing undesired rock from the valuable ore. This lowers the quantity of ore to be processed.
The rocky bodies in the solar system have surfaces of regolith. Regolith is an unconsolidated jumble of loose rock and dust presumably overlying a solid body. Given that the regolith may well be consist of rocks and dust accreted from a distant source, merely assaying the regolith might not reveal the minerals that could be there in abundance just below the regolith. There is no way around it- core samples will be needed to properly assess the economic geology.
PGM Mining on Earth
A look at the large-scale Platinum Group Metal (PGM) production activity in South Africa is instructive. The Bushveld Igneous Complex (BIC) near Limpopo and North-West provinces contains some of the richest PGM deposits in the world. The BIC is found in the Kaapvaal craton. The BIC also extends into Zimbabwe.
The Bushveld complex is located on a ‘craton‘ which is a section of continental crust that has been stable for 400 million years or so. Over that time period some portion of crust has not been subjected to subduction or rifting as an effect of continental drift. A craton is relatively untouched by continental drift over some lengthy time interval and as a consequence the crustal rocks found in a craton may be quite old. Here, ‘old’ means rock that has not been metamorphosed recently, vented out of a volcano or eroded and stratified in a sedimentary formation within several hundred MA.
The Bushveld complex is found in the Kaapvaal craton of South Africa, extending into Zimbabwe. A consequence of this location on a very stable parcel of continental crust is that vertical transposition of rock formations, i.e., subduction activity, has not led to metamorphism or folding of strata. This stability has allowed a relatively undisturbed magma chamber to form and cool, producing layered cumulates.
The formation of cumulates is a partitioning process within the magma chamber that produces solid minerals that can float or sink within the magma. Cumulates with higher density than the magma will tend to sink, building a layer, and lower density minerals will float to the top of the chamber and form an upper layer. In this way, minerals can self-purify and stratify by fractional crystallization.
While fractional crystallization can result in enhanced purity of specific minerals, the melt from which the crystals precipitate is also changing in composition. Magma is a viscous fluid and its components can undergo anion/cation exchange to produce new minerals upon further cooling. Anions include silicate, aluminate, sulfide, hydroxide, chloride, oxide, and a whole basket of metal oxyanions like titanate, tungstate, molybdate, chromate, etc. Cations include most every metal, sometimes including the noble metals. Every metal has a set of positive oxidation states that may be subject to reduction or oxidation to afford a different oxidation state or charge.
While both anions and cations present in magma have a particular charge, their individual size is important as well. Size and charge matter most when crystals are assembling. When, for instance, a calcium-containing mineral is crystallizing, the crystal lattice is subject to collisions with the whole gamut of species in the magma. If the temperature and pressure are appropriate, calcium (+2) cations nestle into a vacancy in the lattice. This is controlled by the concentration, temperature and Gibbs energy of the placement of the cation. However, if a different cation of +2 charge and similar ionic radius happens by, that different +2 cation may find itself occupying calcium’s place in the lattice. An example would be where the Ca+2 cation was replaced by Mg+2 or Fe+2.
Mineral crystal formation is a type of equilibrium wherein lattice anions and cations at the surface of the crystal are in equilibrium with anions and cations in the melt. The rate of crystallization or dissolution is driven by several things. Substitution of a Ca+2 ion in a lattice with Mg+2 or Fe+2 ions retains the charge balance in the lattice. But if a too large or too small +2 cation attempts to sit in place of Ca+2, a mismatch occurs which may be energetically favorable, but as a result may be much more prone to removal by equilibration. The interloping cation could be of such a size that its heat of formation is small and therefore subject to replacement by equilibration. Or not. The resulting mineral could be comprised of Ca+2 cations and M+2 cations in a non-stoichiometric ratio. Or a new mineral comprising a stoichiometric ratio of both cations.
The anions in a mineral substance can be quite varied and several may exist in a mineral at the same time as in the case of anions silicate and aluminate.
The Stillwater Igneous Complex in Montana, USA; the Sudbury Basin in Canada; and the Norilsk-Talnakh deposits north of the arctic circle on the Siberian Craton.
Russia is the leading producer of palladium with 40 % of the global market. Norilsk Is also known as a center of non-ferrous metallurgy as well as noble metals. Norilsk Nickel, also known as Nornickel, is a mining and smelting company. Platinum Group Metals (PGM) have been recovered as a side stream of nickel and copper mining by Norilsk Nickel.
The aerospace proponents of asteroid mining should spend some time at an actual mine. Breaking rock and hauling it around is simple on Earth but consider doing this in a vacuum at near-zero gravity. Look at all of the methods of conveyance and processing in operation at a mine that works only in a gravitational field. Blasting, front-end loaders, haul trucks, conveyor belts, crushers, ball and rod mills, flotation and settling tanks, lixiviation in sulfuric acid and several shifts of staff to operate and maintain it. Don’t forget the analytical lab and chemist or the maintenance group.
Proponents will always say that with the right technology, asteroid mining could work. But in the airgap between could and will is the nagging question of why? Maybe asteroid mining is best left to our descendants in the 22nd century.
A human trip to an asteroid, which is always in orbital motion and probably rotating, to mine and return with paydirt for the investors will always be high cost. Bodies outside of the Earth-Moon system will be nearby only for a short time, depending on the orbital period of the asteroid. While our Earth is measurably overheating, the biosphere is disintegrating and political turmoil is rampant on Earth, perhaps we should focus closer to home?
Humanity must stay focused on critical housekeeping activity here on planet A. Monetizing the outer worlds can wait.
I do believe that eventually somebody will design mining technology to solve the unique problems of mining smaller asteroid bodies with negligeable gravity. Energy dense power sources will be needed to move commercial scale machines and ore. The big problem will be the economics. What mineral is so valuable as to justify the trillion-dollar expense of finding an asteroid with suitable quantities of mineral, up front R&D costs, and beneficiation and isolation of the mineral?
Minerals dispersed in the regolith matrix will need comminution, extraction by lixiviation, floatation, isolation and packaging. Now, we can get it back to earth orbit but then what? Do we just deorbit in the usual way?
Bringing home the paydirt
Let’s say they return 1000 kg (contained) of rhodium valued at todays price of $5400/toz (toz = troy ounce). 1000 Kg contained of rhodium = 32150.7 troy ounces, so 32150.7 toz x $5400/toz = $173,613, 780. However, just the rumor of 1000 kg of new rhodium about to come on the market will drive rhodium prices down. So, $174 million sounds like a lot of money and in a sense it is. But in aerospace and heavy industry, millions are quickly consumed.
Rhodium was chosen for its general scarcity and high price. There is no reason to suppose that rhodium will be more abundant on a given asteroid than on earth so numerous asteroids may need exploration by geologists. Core samples might be needed for the economic geologists to sketch out the size and value of an ore body.
There will be a threshold price of rhodium that must me exceeded before rocket launching and asteroid digging begins. This is how mining works on earth. Until then, the celestial rhodium discovery will just keep orbiting the sun into the future.
An aspect of PGMs is that the very few mines that produce them do so in a unique geological feature on a craton. The mechanism for PGM mineralization in districts like the Bushveld Igneous Complex in South Africa took place in a magma chamber where over time the magma began to cool. Magma gets its minerals from the mantle far below and from the walls of the magma chamber. In subduction zones the subducting crust is pushed downwards causing rising temperatures.
Subducting oceanic crust is loaded with water in several forms. Many minerals are ‘hydrated’ meaning that one or more water molecules are strongly attached to the mineral. These might be called coordinated water. The oxygens are strongly attracted to a cationic feature of the mineral. Interstitial water molecules may be occupying voids in the mineral lattice. Discrete water is only weakly attached and may diffuse elsewhere. Interstitial and discrete water may evaporate readily if exposed to air or heat. At the elevated pressures and temperatures of magma at depth, the three kinds of water are hot enough to flash to steam if the pressure was released. However, as the magma rises to the surface to cooler surroundings and lower pressures, eventually the water will flash to the gas phase moving magma in the direction of lower pressure. Just below the surface the dissolved gases including CO2, steam and SO2 will expand as a gas and push magma to the surface causing a volcanic eruption.
As the magma cools, the substances with the highest melting point begin to crystallize. If the crystals that have a higher density than the magma, they will settle lower in the magma chamber and form a distinct layer. While this layer is building, other minerals will follow in a similar process. The layers of precipitated minerals are called cumulates.
The process of minerals selectively crystallizing and precipitating to the upper or lower zones of the magma chamber. The overall process is called fractional crystallization and layers called cumulates can form. In the photo below are several layers of dark chromite cumulate.
Now that I have expressed my doubts about asteroid mining, I must ask ‘Am I being a Luddite’? Maybe a little bit, but even the doubts of a Luddite can be on the mark now and then. Asteroid mining will be an adventure for a few astronauts, profitable for aerospace contractors and an entertainment spectacle for the public; however, resources seem better used on Earth for remediation of the biosphere, diplomatic solutions for the conflict of the week, lower hydrocarbon consumption and better education, especially in the area of civics.
The whole purpose of mentioning PGM geology and mining in a post titled Asteroid Mining is that we on Earth are fortunate to have concentrated mineral deposits that exist only because of unique geological processes. These processes only work in Earth’s gravitational field. The upwelling of lower density hot hydrothermal fluids. The formation of evaporites rich in borax. Lithium brines.
Take my uranium, please
The formation of cumulates in lava chambers relies on differential density driven by gravity. The ability of rain and snow runoff to mobilize gold sulfides will produce lode gold and placer deposits. The ability of oxygenated meteoric water to oxidize insoluble U4+ to soluble U6+ in sandstone formations to form concentrated roll front deposits. The ability of oxygen to switch uranium oxidation states from U4+ to produce a soluble form (U6+) that can migrate and concentrate leading to the partitioning of U6+/U4+ species. Underground formations of uranium can be dissolved in a solution of sodium bicarbonate by injection and pregnant solutions of the uranium carbonate can be brought to the surface as a solution. This solution is run through a column of ion exchange resin beads which exchange chloride ions for the uranium complex. Once loaded, the beads are washed with a special solution to remove the uranium (6+) concentrate.
Our ability to mine and isolate minerals is uniquely enabled by planet earth. The ability of nature to dissolve, mobilize and concentrate minerals into ore bodies from highly dispersed placement in source rock has been positive for humanity. A great many elements are found in a dispersed condition in the continental crust. For some, there are natural processes for concentration. For others, they form secondary minerals that end up mined with the primary ore. A few like gallium, indium and bismuth are valuable but are only available as a side stream from the primary ore. Copper is an excellent example of a primary metal whose ore includes many other metals like zinc and bismuth. Copper can be electro-refined to 99.99 % purity. The slimes left behind after the electrolysis and dusts caught in ventilation systems can be enriched in useful metals and are often collected for processing.
The purpose of citing the large-scale processes in use on the home planet is not to suggest that asteroid mining must start out at large-scale. It would likely start out as a small-scale surface or underground operation with a small crew or with robotics. Only a few select minerals would be economically suitable for recovery. Platinum Group Metals are mentioned above because of their high intrinsic value and ability to exist as the native metal. If luck is with the astro-miners, the motherlode might be easily visible so later the gangue material can be chipped off. The process of trimming ore to retain the value and discard the gangue was called ore dressing. Being quite dense, the volume of PGM metal ore may be low, but the density and mass is quite high.
If a given asteroid has never been part of a larger system with magma and sufficient gravity to force stratification by density, the cumulate model may not apply. A given asteroid having never been exposed to bulk water and consequently never been subject to hydrothermal flows and weathering may not have minerals that here on Earth are known to be formed with water or partitioned as a result of hydrothermal flows. Lake and ocean sedimentary units are almost surely absent as are processes requiring aqueous migration through porous rock as in the case of uranium roll fronts.
Asteroid mining will be a totally new activity and most all of the natural geological processes on earth will have been absent. Many geological processes on earth produce economic ore bodies. These will be largely absent on an airless, dry asteroid.
One thing to consider: Most of the rock accessible at the Earth’s surface is not economic ore. The surface of the Earth brimming with carbonates, silicates and aluminates bound to a variety of ‘ordinary’ metals like calcium, magnesium, iron, sodium, potassium and a handful of other common metals. While there are important and valuable uses for these common metals, they are predominantly found dispersed in surface rock comprised of many individual minerals, or that an ore body is too small for economic recovery.
The fraction of the desired mineral in the ore can be highly variable. Depending on the market, some parts of the ore body may be economical to mine while other parts may not. This is why cores are drilled to locate the 3-dimensional extent of the ore body, estimate the potential value and minimize the expense of digging and processing uneconomical ore.
It seems reasonable to suppose that, just as much of the surface of the earth is covered with rocks made from mineral constituents of low economic value like crushed roadbed rock or sand and cement for concrete use, why should we assume that a given asteroid would be any better endowed with value than Earth’s surface? Asteroid mining will necessarily be preceded by expensive exploration. Obviously, right? But it means that considerable money and time will be spent up front finding an asteroid that is sufficiently ‘pregnant’ with valuable metal ore. Finding investors to fund exploration and mining development today is based on economic geology surveys and signed off by certified experts.
A mine is a hole in the ground with a liar standing at the top. –Attributed to Mark Twain
On Earth many mineral deposits have been located historically by surface exposures that are part of a larger ore body. The economics of isolating any one mineral or metal in the presence of the others will depend heavily on the % concentration of the target mineral, the processing methods available and the market price of the final product. A market downturn can last months, years or represent new long-term realities in demand for the product.
The red sandstone walls of Red Rocks Amphitheater outside of Denver, Colorado, were mistakenly painted blue instead of bright orange this week. The painting vendor, Biff’s Garden Center of Peculiar, MO, has not yet issued a statement regarding the mistake.
The Denver Regional Council of Governments (DRCOG) is trying to convince the Bronco organization that a new stadium is not necessary because overflow crowds can watch the Broncos on wide screen television at the amphitheater instead. DrCOG’s hope is that the redecorated amphitheater and extortionate concession prices will deflect attention from efforts to finance a new stadium.
Denver International Airport (DIA) famously has a large statue of a blue mustang with bright red glowing eyes. It’s known locally as Blucifer and opinions of it are extreme either way. The artist who sculpted the statue, Luis Jimenez, was killed in 2006 when part of it fell on him, severing an artery leading to his exsanguination in his studio.
Blucifer can only be seen from Pena Boulevard on the drive in or out of DIA.
Poltroon University will be hosting the 15th Annual Easter Chemical Parade in Guapo, Arizona, on Sunday, 20 April, 2025. Former Arizona Governor Barbara Hoskins will serve as Parade Marshal.
Advanced dye formulations will be on display coloring the floats and decorating the Poltroon MacGuyver Convention Center. Local manufacturers like Tuscon Anilin und Soda Fabrik (TASF) will graciously provide sparkly rare earth pigments for the youngsters to dye their eggs in a large playground vat.
The fairgrounds will feature entertainment chemistry booths where parents can hold thin layer chromatography elution races of mystery dyes. The fastest elution of the three spots is eligible for a stuffed animal prize. Fire extinguishers are provided.
Another booth will hold fractional distillation races with prizes for the largest heart cut. Contestants must clean their own glassware.
The Klaus Fuchs Uranium Facility will sponsor a uranium Easter Egg hunt looking for a geo-cached easter Egg containing uraninite ore. Playschool Geiger counters will be issued to children over 4 years of age who will search the convention center parking lot for the colorful uraninite eggs.
C’mon Democratic Party!! Don’t waste time trying to convince Schumer to pull his thumb out of his a$$. For everything there is a season and the MAGA win in the November 2024 election marks the end of Schumer’s season and the freshening spring season for MAGA. Out to pasture he needs to go. Maybe he can get an adjunct professor slot at a university teaching economics recitation sections.
It is time for Democrats to match the ferocity of MAGA’s political rhetoric. Being polite, using history and logic or even shaming them is a complete waste of time. They are on a libertarian high from years of carrying forward Reagan’s antigovernment rhetoric.
Civility should always be tried first in any conflict, but continued civility is a fool’s errand in the face citizens who voted for and continue to support Trump’s authoritarianism.
It’s time to get mad. Very mad. Not with violence but with pressure and votes. What the MAGA GOP is presently doing to our beloved country may well be irreversible to some extent. I don’t care to live in a country satisfied with Trump authoritarian leadership. Trump is replacing what he calls the “deep state” with an even darker deep state of his own design. The cult of the Orange Jesus needs to be driven out.
It all boils down to votes. The Dems need an effective ground game to get people to the polls. Political actions that do not produce more liberal or at least anti-MAGA votes is a waste of effort.
Each voting Dem should bring along one liberal non-voter or at least anti-Trump non-voter to the polls the next few elections. The mantra for Democrats should be- “Anti-Trump + 1”.
ANTI-TRUMP VOTER + 1 Encourage a non-voter to vote Democratic!
Robet Reich pointed out in today’s (3/25/25) Substack email that what he calls the Pillars of Civil Society are under attack by the Trump administration. The pillars are- the universities, science, the media and the law.
The legacy media, at least, is covering Trump at roughly the level of entertainment news. There is some tut-tutting and rubber necking by the big news shops like NBC, CBS and ABC. NPR continues to try to be as neutral as possible allowing listeners to decide for themselves what is outrageous. The well-known MAGA friendly broadcasters are
Lamentations on Chemistry 