Episode 389 Vanadium

Vanadium is a metal, and by far its greatest use is in steel alloys, where tiny amounts of vanadium improve steel’s hardness, toughness, and wear resistance, especially at extreme temperatures. As I reported in my book What Things Are Made Of, more than 650 tons of vanadium was alloyed with iron to make the steel in the Alaska Pipeline, and there’s no good substitute for vanadium in strong titanium alloys used in jet planes and other aerospace applications.

Vanadium isn’t exactly one of the well-known elements, but in terms of abundance in the earth’s crust, most estimates indicate that there’s more vanadium than copper, lead, or tin. But it’s difficult to isolate, and it wasn’t produced chemically as a chloride until 1830, when Swedish chemist Nils Sefström named it for the Norse goddess of beauty, Vanadis, perhaps better known as Freyja. It wasn’t until 1867 that pure vanadium metal was isolated by British chemist Henry Roscoe, whose work on vanadium won him the name of the vanadium mica roscoelite.

As a mineral collector, I’m attracted to vanadinite, lead vanadate, because it forms beautiful hexagonal crystals, often bright red and so abundant from one lead-mining area of Morocco that excellent specimens can be had without mortgaging your house. Some vanadinite crystals are like perfect little hexagonal barrels, and others can form needle-like spikes around a central crystal, making the whole thing look like a cactus with caramel-orange spines.

Some of the vanadium for making steel alloys comes from primary mined vanadinite, but much more was once produced as a by-product of phosphorous manufacture, because it’s commonly associated with phosphate rock. And today, a lot of the world’s vanadium comes from refining crude oil and from fly ash residues, which are products of coal combustion. I got curious about why vanadium metal is so closely connected with these organic deposits.

Crude oil actually has lots of trace elements in it, including metals like gold, tin, and lead, but by far the most abundant are nickel and vanadium, as much as 200 parts per million nickel and 2000 parts per million vanadium in some crude oils, especially heavy, tarry oils like those found in Venezuela. In some oil, the nickel and vanadium can add up to 1% by weight of the oil, an incredibly huge amount. Refining Venezuelan crude gave the U.S. a lot of vanadium back in the late 20^th century. But why is it in there?

Oil and coal are both the result of decaying and chemically changing plant matter. Forget dinosaurs; virtually all oil, natural gas, and coal comes from plants – usually marine algae for oil and gas and more woody, land-based vegetation for coal. There’s a class of organic molecules called porphyrins. I’m no organic chemist, but these complex hydrocarbon molecules, made of carbon, hydrogen, oxygen, and nitrogen have boxy ring-like structures with open space in the centers. Chlorophyll and hemoglobin are related chemicals, both of which contain metals in the middle of the structure, magnesium in chlorophyll and iron in hemoglobin. The vacant holes in the centers of porphyrins in crude oil are ideal for trapping metal molecules, and apparently vanadium, in the form of a VO2 ion, is one of the easiest to trap because of its molecular size and electronic valence.

The vanadium comes from the original oil source rock, so there’s quite a range in vanadium content around the world. Heavy oils, like the tars in Venezuela, hold more than fluid oils like those in Saudi Arabia. This has more or less been known since at least the 1920s, and today the vanadium and other metal contents of oils are being used to characterize the original source rocks even when those source rocks no longer exist or are no longer what they once were.

The United States has had no mine production of vanadium since 2013 and even then we were 94% dependent on imports. Today 100% of our vanadium is imported, and we also produce some vanadium from imported crude oil and ash. More than 90% of the world’s vanadium is mined in China, Russia, and South Africa, although the US imports much of what it needs from the Czech Republic and Canada as well as Russia. We also imported enough ash and refining residues to account for 9000 tons of vanadium in 2015, mostly going as I said to making steel alloys. A new emerging use is in high-capacity storage batteries, where vanadium compounds make the electrolyte. These batteries have potential uses for renewable energies such as wind and solar power, and although in 2015 and 2016 several companies were working on prototype designs, they’re still pretty expensive batteries.

Way back in 1971 when I was a teaching assistant for the Indiana University Geologic Field Station, on one mapping project we went to the Mayflower gold mine south of Whitehall, Montana. I collected a bunch of rocks with interesting looking sparkly crystals – some of which I’ve only recently gotten around to really studying. I gave a talk at the 2017 MontanaBureau of Mines and Geology Mineral Symposium on minerals from there that turned out to be vanadium-bearing, including vanadinite, although it’s probably an arsenic-rich variety, and stranger minerals like descloizite, a lead-zinc vanadate, tangeite, calcium-copper vanadate, and some others. I even think there are some tiny bits of roscoelite, the vanadium mica named for the chemist who first prepared vanadium metal.  

Even more exciting for me are some tiny, millimeter-sized red-orange crystals in the specimens I found at the Mayflower Mine. All I knew for a long time was that I couldn’t figure out what they were. By looking at their crystal shapes and properties, I narrowed it down to two very strange and very rare minerals – gottlobite, a calcium-magnesium vanadate, and calderónite, a lead-iron vanadate. Both of these minerals are so obscure I didn’t really seriously imagine I had actually collected one of them. But, thanks to an analysis by Stan Korzeb, the economic geologist at the Montana Bureau of Mines and Geology, it turned out that I did indeed find calderónite, 32 years before it was described as a new mineral in 2003. Stan’s analysis in January 2018 used EDX, or energy-dispersive x-ray spectroscopy, a technique that gives not only the elements present in a mineral, but their relative proportions, which allowed Stan to calculate the chemical formula. The lead-iron vanadate calderónite he found is intergrown with descloizite, a lead-zinc vanadate. This probably indicates changing iron-zinc concentrations in the fluids that precipitated the minerals. This represents just the 11^th documented calderónite occurrence in the United States and the second in Montana. Stan identified the first in Montana in the fall of 2017.

It’s an obscure mineral, and the crystals are tiny, but it made this mineral collector’s day.

—Richard I. Gibson

Link:

USGS Mineral Commodities - Vanadium (PDF) 

Episode 388 Folds in Algeria

You may have seen some of the spectacular images of the earth in southern Algeria, curves and colors like some Picasso in the opposite of his cubist period. If you haven’t, check out the one from NASA, below. 

The ovals and swirls, with their concentric bands, are immediately obvious to a geologist as patterns of folds, but not just linear folds like many anticlines and synclines form. These closed ovals represent domes and basins – imagine a large scale warping, both up and down, in a thick succession of diverse sedimentary rocks, like sets of nested bowls, some of them right-side up and some inverted, then all sliced off halfway through.

But “obvious to a geologist” has plenty of limitations in a space image. Without knowing more information, it’s difficult to be sure if an oval is a basin or a dome. And you can speculate, but without some ground truth, it’s challenging to be sure what the rock types are.

Ahnet-Mouydir, Hoggar Mountains, Algeria. NASA image - source

This area, called the Ahnet-Mouydir, on the flank of the Hoggar Mountains close to the middle of the Sahara Desert, is remote, inhospitable, and arid, and called the “land of terror” for a reason. The rocks represent a thick sequence of marine sandstones, shales, and limestones, spanning a huge range of ages, from at least the Ordovician to the early Carboniferous – 150 million years or more, a great chunk of the Paleozoic era.

The core of the Hoggar Mountains is an old Precambrian block, not as big as the cratons and shields that form the hearts of most of the continents, but otherwise similar. It might have been something like a microcontinent that became amalgamated into the growing supercontinent of Gondwana about 600 million years ago. After that amalgamation, seas came and went much like they did in western North America throughout much of the Paleozoic era, laying down the sediments that became the rocks we see today in the northern Hoggar Mountains.

That’s all well and good – but here’s the next question, how did the rocks get deformed into these oval domes and basins? If you imagine the kinds of collisions that are typical on earth, you think of linear or curvilinear things – island arcs, edges of continents and such – that when they collide, are likely to make linear belts of deformation. This is why so many mountain ranges are long, linear features, and the folds and faults that make them up also tend to be linear. Domes and basins happen, but that seems to be almost all we have here in these mountains.

We have to look for a deformational event that is later than the youngest rocks deformed. So if some of these rocks are as young as early Carboniferous, about 340 million years old, the mountain-building event that fills the bill is the Hercynian Orogeny, where ‘orogeny’ just means mountain-building.

The Hercynian, at about 350 to 280 million years ago, represents the complex collision between Gondwana and the combined North America and Europe, which were already more or less attached to each other. The leading edge of Gondwana that collided was in what is now North and West Africa, and the collision produced mountain ranges all over – the Alleghenies in the central Appalachians in North America, and a complex swath of mountains across central Europe, from Spain, across France to northern Germany and into Poland, as well as elsewhere. In Africa, the most intense squeezing was at the leading edge, in what is now Morocco and Mauritania, colliding with North America, and northern Algeria, impacting Iberia.

The basins and domes of southern Algeria that we’re trying to understand are 1500 kilometers or more from that leading edge of continental collision. So I think – and full disclosure, I’ve never really researched this area in detail – that what must have happened is that that distant hinterland wasn’t pushed into tight, linear belts like those we find along the lines of collision, but the force was enough to warp the sediments into these relatively small domes and basins. Alternatively, it might be possible that the brittle Precambrian rocks beneath the sedimentary layers broke from the force of the collision, so that the sedimentary layers draped over the deeper brittle surface like a carpet lying over a jumble of toy building blocks – some high, some low.

The latter idea, that the brittle basement rocks were broken and pushed upward with the sedimentary layers draped over them is supported by research published in the journal Terra Nova in 2001. Hamid Haddoum and colleagues studied the orientations of folds and faults in this area, trying to figure out the orientations of the stresses that caused them. Their data show a shortening direction – which means compression, or squeezing – during early Permian time oriented about northeast-southwest. That is consistent with the collision that was happening at that same time between what is now Senegal and Mauritania, in westernmost Africa, and the Virginia-Carolinas region of what is now the United States. Haddoum and his colleagues show cross-sections with basement upthrusts, basically high-angle reverse faults where older rocks are squeezed so much that they are pushed up and over younger rocks. This is quite similar to the Laramide Orogeny in the western United States about 80 to 50 million years ago, but this compression was happening about 280 million years ago as the supercontinent of Pangaea was assembled during the early Permian Period. Both represent deformation at relatively great distances from the lines of continental collision. In the case of the Laramide in western United States, one idea for transmitting the stress so far from the collision is that the subducting slab of oceanic crust began to go down at a relatively gentle angle, even close to horizontal, creating friction and stress further away from the subduction zone than normal. Whether that’s the case here in southern Algeria isn’t clear for this Hercynian collision.

I wouldn’t think of this area as high mountains, such as those that must have formed along the lines of Hercynian collision. Maybe more like warped, uplifted plateaus – but whatever they were, they were certainly subject to erosion. Erosion probably wore the domes and basins down to a common level, so that the nested bowls were exposed in horizontal cross-section – which for geologists is the equivalent of a geologic map. And that’s what the beautiful photos reveal.

The area might have been planed off even more by Permian glaciers during and after the Hercynian mountain-building events. But then, during the Mesozoic era, seas returned to the region and all this mess of eroded domes and basins was buried beneath even more sediments. Sometime relatively recently, during the Cenozoic era, the past 65 million years, everything was uplifted at least gently, so that the highest parts – including today’s Hoggar Mountains, were stripped of the younger Mesozoic sedimentary rocks, revealing the much older Paleozoic rocks in the domes and basins.

—Richard I. Gibson

Link: 

Haddoum, H., Guiraud, R. and Moussine-Pouchkine, A. (2001),Hercynian compressional deformations of the Ahnet–Mouydir Basin, AlgerianSaharan Platform: far-field stress effects of the Late Palaeozoic orogeny.Terra Nova, 13: 220–226. doi:10.1046/j.1365-3121.2001.00344.x

Episode 387 Geology of Beer

It isn’t true that all geologists drink beer. But many do, and I’m one of them. Today I’m going to talk about the intimate connection between geology and beer.

Beer is mostly water, and water chemistry has everything to do with beer styles. And water chemistry itself depends mostly on the kinds of rocks through which the water flows. You know about hard and soft water – hard water has more dissolved chemicals like calcium and magnesium in it, and while salts of those chemicals can precipitate out of hard water, making a scum on your dishes, they also can be beneficial to development of bones and teeth. In the United States, the Midwest and Great Plains have some of the hardest water because of the abundant limestones there, and in Great Britain, southern and eastern England have harder water than Scotland for similar reasons.

But it wasn’t limestone that made Burton-upon-Trent a center of brewing in the 19^th Century, when it was home to more than 30 breweries. The water there is rich in sulfate which comes from gypsum, calcium sulfate, in the sandstone underlying the region. Those sandstones are Permian and Triassic in age, representing a time when much of the earth was arid. Those dry conditions allowed gypsum to crystallize in the sediments. Gypsum is much more soluble than limestone, and the slightly acidic waters of Burton help with that. Burton water has ten times the calcium, three times the bicarbonate, and 14 times the sulfate of Coors’ “Rocky Mountain Spring water” in Colorado. That certainly makes Coors’ Burton brewery product rather different from that made in Colorado.

In fact, the addition of gypsum to beer is called “Burtonization.” This increases the hops flavor, but more important to history, sulfates act as preservatives in beer, enough so that Burton brews of pale ales could survive the long trip to British India, giving us the India Pale Ale style of beer. Not from India, but brewed with sulfates derived from gypsum in Britain’s rocks.

That slight acidity in Burton’s water depends on the calcium and magnesium content, and also lends itself to extracting sugars from malted barley in the mashing process. Calcium and magnesium also help yeast to work its magic. Today, home brewers can buy “Burton Water Salts” to imitate the product from England.

Truman, Hanbury, Buxton & Co., Black Eagle brewery, Derby Street, Burton-upon-Trent, in 1876,
from University of London

Less hoppy beers often originated in areas where the sulfate content of the water was low. Pilsen in the Czech Republic, home to pilsner beer, has almost no sulfate and only 7 parts per million calcium in its water, compared to around 300 for Burton. Pilsen is in an area of metamorphic rocks that don’t yield the typical hard-water-making elements.

The presence of Carboniferous age limestones in Ireland make waters that are high in calcium and carbonate, but they lack the sulfate of northern England. Together with other differences, that makes the area around Dublin ideal for making a stout porter known today as Guinness.

After water, it’s the soil that makes the most difference to beer. Hops can grow in a wide range of soils, even the decomposed granite we have here in Butte, but the thick, well-drained soils of Washington and Oregon, weathered from volcanic rocks, make those states the source of 70% of the hops grown in the United States.

The surge of craft breweries in the United States has given rise to some interesting geological names for brews. Great Basin Brewing in Reno and Sparks, Nevada, has Ichthyosaur IPA, known as Icky, as well as Orogenesis, a Belgian-style amber ale. Socorro Springs, in New Mexico, brews Isopod Pale Ale and Obsidian Stout is available from Deschutes in Oregon.  You can get Triceratops Double IPA at Ninkasi Brewing in Eugene, Oregon, and Pangaea Ale at Dogfish Head in Delaware. And even though it’s more chemical than geological, we shouldn’t leave out Atomic Ale’s Dysprosium Dunkelweizen, made in Richland, Washington. Dysprosium is a rare-earth element found in the phosphate mineral xenotime and other stranger minerals.

San Andreas Brewing Company, near the fault in California, boasts Oktoberquake and Aftershock Wheat.

And I’m undoubtedly prejudiced, because I’m the House Geologist at Quarry Brewing here in Butte, which probably has the best mineral collection in a brewery in the United States, but I think their collection of geological names for their beers is unexcelled: Shale Pale Ale, Galena Gold, Open Cab Copper, and Gneiss IPA, and seasonals including Albite, Basalt, Bauxite, Calcite, Epidote, Halite, Ironstone, Porphyry, Opal Oktoberfest, Schist Sour, Rhyolite Rye Pale Ale, Pyrite Pilsner, and more. Mia the bartender and I tried to come up with a fitting name for a 50-50 mix of basalt and gneiss. I wanted it to be charnockite, but we ended up calling it Mia’s Mixture.

Next time you enjoy a beer, thank geology!

—Richard I. Gibson

More Geology of Beer 
And another from Lisa Rossbacher

Image: Truman, Hanbury, Buxton & Co., Black Eagle brewery, Derby Street, Burton-upon-Trent, in 1876 from University of London

Paleozoic Vertebrates compilation

Ganoid fish from an old textbook (public domain)

Running time, 1 hour. File size, 70 megabytes.

This is an assembly of the 15 episodes in the original series from 2014 that are about Paleozoic vertebrates.

I’ve left the references to specific dates in the podcast so that you can, if you want, go to the specific blog post that has links and illustrations for that episode. They are all indexed on the right-hand side of the blog.

Thanks for your interest and support! 

Episode 386 Dynamic Topography

What is dynamic topography? Well, it depends on who you ask. Dynamic topography is similar to other terms, like uplift, that have been used in so many different ways that you really have to look at the document you’re reading to understand what the author is talking about. This term has been applied to places around the world, like the Colorado Plateau in the United States, South Africa, the Aegean, and East Asia, which makes it even more complicated to tease out its meaning.

Most broadly, dynamic topography refers to a change in the elevation of the surface of the earth in response to something going on in the mantle. This “something” can include both the flow of the mantle, as well as differences in mantle temperature or density. For the purposes of this podcast, I will use a more strict definition: Dynamic topography is the change in the elevation of the surface of the earth in response to the upward or downward flow of the mantle.

How much higher or lower can dynamic topography make the earth’s surface? Well, that’s a matter of debate. Earlier studies have suggested that several kilometers, or over 6000 feet of modern elevations can be explained by things going on in the mantle. More recent work instead suggests that dynamic topography creates changes of at most a three hundred meters, or a thousand feet.

A good example of a place where this process is thought to be active is Yellowstone. As Dick Gibson discussed in the December 19th, 2014 episode, Yellowstone is thought to be a hot spot. That is, an area of the earth where hot material moves from deep within the mantle to the base of the crust, causing significant volcanism at the surface of the earth. Other well-known hot spots are located in Hawaii, and Iceland.

So how can a hot spot like Yellowstone cause dynamic topography? Well, you’ve probably seen a similar process at play the last time you played in a pool or a lake. Think of the surface of the pool like the surface of the earth. If you start moving your hands up and down under water, the surface of the pool starts to move up and down. If you ever tried to shoot a water gun upwards underwater when you were a kid, you probably remember it pushing up the surface of the water, and being disappointed that it didn’t shoot out at your friend or sibling. As an adult, you could try holding a hose upwards in a pool. Again, it probably won’t shoot out, but will gently push upwards on the surface of the pool.

Dynamic topography concept. © Commonwealth of Australia (Geoscience Australia)
 2017, used under Creative Commons Attribution 4.0 International Licence 

The principle for a hot spot creating dynamic topography is the same. The flow of the mantle pushes upwards, warping the crust and increasing the elevation of the earth’s surface above the hot spot. Near Yellowstone, this results in an area of high elevation which lies next to the Snake River plain.

But Dynamic Topography doesn’t just cause increases in elevation, it can also pull the earth’s surface downward. In North America, dynamic topography is thought to have been in part responsible for the creation of the Cretaceous interior seaway. 

As a reminder, the Cretaceous interior seaway was a shallow sea that covered parts of western North America, in middle to late Cretaceous time, about 100 to 79 million years ago. Its size varied, but at its greatest extent the seaway stretched through Texas and Wyoming in the US, and Alberta and to the Northwest Territories in Canada. It was widest near the US-Canadian border, where it stretched from Montana to western Minnesota.

Low elevations in western North America that allowed the ocean to flood in and form this shallow sea may have been caused by downwards flow in the mantle. This downwards flow was likely caused by oceanic crust that was subducted at the western margin of North America. That is, oceanic crust that went underneath the North American plate and into the mantle. Because this crust was part of the Farallon oceanic plate, it is often referred to as the Farallon slab.

As oceanic crust associated with the Farallon plate continued to sink into the mantle, it continued to cause changes in the elevation of North America. This drop in elevation likely decreased in size as the Farallon slab moved towards the eastern edge of North America, and deeper into the mantle.

Since Eocene time, or about 55 million years ago, dynamic topography associated with the Farallon slab is thought to have been in part responsible for lower elevations in the eastern United States. A wave cut escarpment called the Orangeburg Scarp is now located 50 to 100 miles inland from the coasts of Virginia, Georgia and the Carolinas. It formed at sea level and now lies up to 50 meters, or about 165 feet above the modern coast line. In fact, a good part of the southeastern US to the east of this escarpment contains marine sediments, and smooth topography as a record of its time underwater.

Differences in the elevation of the Orangeburg Scarp along its length suggest that rather than just going up and down, the Atlantic coast experienced a broad warping caused by mantle flow. The most recent phase of warping brought this area to modern elevations, as warm material moved into the upper mantle beneath the Atlantic coast. This warm material helped push the crust up to higher elevations, creating the southeastern US as we see it today.

This example also highlights an important part of dynamic topography: If you are already at really high or really low elevations, you might not notice it much. If you are near the coast, it can have a big impact as the sea starts to flood in and out due to changes in the mantle. Provided of course, you’re there for the millions to tens of millions of years it takes for the mantle to flow this way and that. That’s why geologists typically rely on the rock record to provide evidence for processes like dynamic topography.

—Petr Yakovlev

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This episode was recorded at the studios of KBMF-LP 102.5 in beautiful Butte, Montana. KBMF is a local low-power community radio station with twin missions of social justice and education. Listen live at butteamericaradio.org.

Links:

What is Dynamic Topography?

Surface expressions of mantle dynamics

Dynamic topography, eastern US