This is an I Heart Podcast. Guaranteed Human. She needs some money, she's got a great idea, she's in the car park, runs up to the van, GO! Score some easy money by selling your unwanted gold to Gold Arthur. Gold Arthur will buy your gold at the right price. Look out for the Gold Arthur van, near you. Book your free valuation at goldArthur.co.uk Gold! Go to freetrade.io slash radio to get started. Capital at risk, Isar and Sip Rules apply, other charges may apply. Happy Saturday! This week we talked about rickets and vitamin D, and we mentioned that in 1669, Hinnig Brand figured out what phosphorus was by boiling urine. A lot of it. We have a whole episode about that, it came out on April 29th, 2019 and it is today's Saturday Classic. At the beginning of this classic we talk about an event called Bawfest. It doesn't seem like there's been one of these in the past few years, but there are still some videos from earlier ones available on YouTube if you want to check them out. So enjoy! Welcome to Stuff You Missed in History class, a production of I Heart Radio. Hello and welcome to the podcast, I'm Tracy V. Wilson, and I'm Holly Fry. Every year there's a thing in Cambridge, Massachusetts called Bawfest. It's held in other places too, but the wedding Cambridge on the MIT campus is the one that I go to. It's the festival of bad ad hoc hypotheses. It's a place where people present their scientific papers, except the scientific papers are fake and also funny, and very well-argued and sometimes really plausible on top of being so hilarious. So like for example, last time the winning talk was all about the role of noise in the spread of bubonic plague in the 14th century and it was accompanied by a whole lot of pictures from illuminated manuscripts. And I don't want to get into more detail than that because they put videos of all these things online. And I want anybody who goes to watch it to see all the hilarious reveals firsthand. It is often a very cool blending of science and history and fakery and hilarity altogether. And the reason I'm talking about this is that the winners of this very silly nerdy thing used to get a 3D printed representation of Darwin looking doubtful. But now they get a trophy of Henning Brand discovering phosphorus. Henning Brand discovered phosphorus by boiling pea. So the first time I heard about this at Boffest, I was like we got to do a podcast on that. It has just taken me a few years to actually get to it. In case it was not clear, this episode is going to have a lot of urine in it. Hurray! I love a pee joke. They're very funny to me because I'm crass. One of my cousins has a daughter who's just at the age to be having sleepovers and at the age mentioning of any bodily function is just instantly hilarious. I remember as a kid, if somebody was like, Pepee! It would just send everyone into giggles forever. Yeah, it was very different as a child. You know, I was raised with a lot of shame about your body and anything it might do or predict. It wasn't until I became a little bit older and out in the world where I was like, you guys urine is really funny. But as a child, if you said something about pee at a sleepover, there would be mortification and like, oh no! It's a very different culture. Yeah, yeah, yeah, yeah. A little Victorian in my house in that regard. It's a matter in hand. Bosphorus is a chemical element. And if you need a quick chemistry refresher, elements are a basic building block of matter. And elements are made of atoms and atoms are made of subatomic particles, but you cannot take those subatomic particles out of an atom by ordinary chemical means. A pure piece of an element like phosphorus is made of phosphorus atoms. And one atom of phosphorus is the smallest piece of phosphorus that you can get. Yeah, I'll take one phosphorus, please. When I wrote that, I made it almost sound like all elements are made of phosphorus. That's not it's that all elements are made of atoms of that type of element. And so several chemical elements were known to the ancient world. You'll see slightly different lists depending on where you look, but in general, humans have known about gold, silver, copper, iron, lead, tin, zinc, arsenic, antimony, mercury, sulfur, and carbon for thousands of years. Pretty much any ancient culture that has written records, names at least some of these in those records. These elements have all been known about for so long that we could not really say who discovered them, or who first concluded that there was anything special about them. Phosphorus, on the other hand, is the first element whose discoverer we can name, and that was Henning Brand in about 1669. But unlike most of the other elements we just listed, phosphorus doesn't exist in its pure elemental form out in the natural world. It's extremely reactive, so instead, it's found in phosphate compounds. Those compounds are used to produce elemental phosphorus, which is called yellow phosphorus. White phosphorus can then be used to make more stable alitropes, including red and black phosphorus. In casual use, the words phosphorus and phosphates are used almost interchangeably, sort of like how people say carbon to mean carbon dioxide. Phosphates are fundamentally necessary to life on Earth. They're part of the structure of DNA and RNA. They're also a component in adenosine triphosphate or ATP, which carries energy within all living cells. Calcium phosphate helps provide the strength in our bones and teeth. So, I mean, it's just not an exaggeration to say that we would be dead without phosphorus. Very squishy. People have also been intentionally using phosphorus for thousands of years before Brand discovered it, without knowing that that was what they were doing. In some parts of the world, the soil doesn't contain a lot of phosphorus, and even in places where the soil starts out phosphate rich, it loses its phosphates and other nutrients over times through farming. For as long as people have deliberately cultivated crops, they've also understood that there was something about the soil that needed to be replenished in order for crops to continue to thrive there. A lot of the strategies people have used to try to make their crops grow better have really been adding phosphorus along with the other essential nutrients of nitrogen and potassium back into the soil. As examples, the practice of burning off the stubble of last year's crop doesn't just clear the land for new planting, the ash also contains phosphorus, which goes back into the soil. People have also fertilized their crops with things like manure, urine, fish, and oyster shells, all of which contain phosphorus and other nutrients. Crop rotation takes advantage of the differences in how different plants use nitrogen, potassium, and phosphorus to try to keep all three of those readily available in the soil. People did things like this for centuries without knowing what phosphorus was or that the crops that they were growing needed it. Ancient people's use of phosphorus also wasn't limited to agriculture. As one example for thousands of years, people have used stale urine to clean things. A big reason for this is that urine contains urea, which decays into ammonia when it's left out for a long time. But urine also contains a lot of phosphates and phosphates help make other cleaning agents more efficient. Please don't take this as a any sort of household cleaning tip. When we were in San Francisco at the end of our tour last year, I went to the Book Binder's Museum. I had a guided tour of the Book Binder's Museum. One of the things that I learned about is how in one element or one part of the book binding printing process, there were these little ink dobers that were sort of leather-covered things that you would dobbin the ink and you would put that in the plate that you were going to print. If that dried out, your apprentice had to go and clean them and start completely over. Part of the apprentice's job was to keep that nice and moist. The tour guide said, do you have any ideas of what they might have used to clean these things? I was like, I bet it's urine because that was the thing that I could think of. In the early days of book binding would probably be something and she specified that it was stale urine. That is for the reason that we just said. So, of course, when Heningbrand was alive, people did not know what phosphorus was or that it was connected to all of this and even after he made his discovery, people didn't really understand what it was he had found. At the time, European scientists still understood the world in terms of not the chemical elements that we think about today, but the four elements of earth, air, fire and water. The field of alchemy was just starting to evolve into the field of chemistry when he lived and the definition of elements was just starting to evolve from those four elements into more like today's definition. And there's more about the shift from alchemy to chemistry in our most recent Saturday classic. But as it relates to Heningbrand, by the 1660s, there were still a few alchemists searching for the fabled philosopher's stone, which was believed to turn base metals into gold and produce an elixir that could cure diseases in prolonged life. And Brand was one of them. Heningbrand's discovery of phosphorus came about because he thought the secret to the philosopher's stone might be found in urine. And we'll get to why he thought that and how he made his discovery after a sponsor break. We do not know all that much about Heningbrand as a person. Sometimes his name is spelled Hening instead of Hening. Sometimes his last name is B-R-A-N-T or B-R-A-N-D-T instead of B-R-A-N-D. He was probably born in Hamburg and what's now Germany. Sometime around 1630, he seems to have spent some time as a low-level army officer during the 30 years war. And that suggests that he was from a middle-class family because he was an officer. So probably they were not very poor, but also he was not of a very high rank, so they probably weren't all that prominent either. In addition to his army service, Brand seems to have done at least part of an apprenticeship with a glass blower before turning his attention to alchemy. This would have given him the skills to make some of the glass vessels used in alchemy, and a glass blower's furnace would have been useful to his alchemical pursuits as well. At some point in all of this, he married a woman whose dowry was large enough to fund his research. After Brand's first wife died, he remarried a woman named Margueretta, who had also been married before. Her son became Brand's assistant in his workshop and her family's money continued to pay for all of his experiments. He may have also presented himself as a physician, although according to a 19th century history of chemistry, he was quote, an uncouth physician who knew not a word of Latin. As we said before the break, Brand was looking for the philosopher's stone, which was believed to turn basementals into gold and produce the elixir of life. Many alchemists believed that the key to the philosopher's stone was somewhere in human bodily fluids. And the fluid that Brand focused on was pee. Not only is urine a bodily fluid, but it is also yellow, you know, like gold. To be clear, Brand was not the only person who thought that maybe urine had something to do with gold. Urine was pretty mysterious at the time. Nobody knew how the body produced it or why it was yellow, but they did know that it did all kinds of fascinating and seemingly magical things. We talked about it's uses a cleaning agent before the break, but it was also used in tanning leather and dyeing fabric and in all kinds of alchemical recipes. Urine was also used in some methods of making salt Peter and then the salt Peter was used to make gunpowder. So part of gunpowder was from urine. With all of those things going on, it wasn't really that much of a stretch for people to suspect that this strange potent seemingly slightly magical liquid might be yellow because it contained gold. Today though, we know that the yellow color mostly comes from a substance called urebilin, which is one of the end products of the body's breaking down the iron containing molecule heme. Brands experiments with urine involved boiling it over and over in a vessel called a retort. A retort is a spherical vessel with a long downward pointing spout. If you heat up something in a retort, the vapor rises then condenses in that long spout so you can use it to distill things. One day as brand was distilling urine and his retort, the fluid dripping out of the spout started spontaneously bursting into flame and it also smelled very strongly of garlic. And he found if he caught it in a vessel and then stoppered the vessel up, it would glow regardless of whether it had been exposed to any light. I'm sorry to laugh. Brand thought it was funny though. My fiery garlic glow pee. I don't know. The whole thing is very funny. Brand thought that he was on to something, perhaps even the philosopher's stone. So he kept refining his process, producing this white-ish, waxy substance that was very volatile if exposed to air. And it had a blueish glow if it was kept away from air. Here is his recipe for making phosphorus as published in philosophical experiments and observations of the late eminent Dr. Robert Hook, which was published in London in 1726. Since this was almost 60 years after Brand's discovery and recorded by a different person, it is likely that various steps have been changed or added, but this definitely will give you a sense of what always involved in this. So under the heading, phosphorus elementaris by Dr. Brand of Hamburg, it reads, quote, take a quantity of urine, not less for one experiment than 50 or 60 pales full, let it lie steeping in one or more tubs or in a hog's head of oak and wood, till it putrify and breed worms as it will do in 14 or 15 days. Then in a large kettle, let some of it boil on a strong fire. And as it consumes and evaporates pour in more and so on till at last the whole quantity be reduced to a paste or rather a hard coal or crust, which it will resemble. And this may be done in two or three days if the fire well tended, but else it may be doing a fortnight or more. So for one batch of phosphorus, Brand was leaving urine out in pales for about two weeks and then boiling it for between two and 14 days. And that is not the end of the process. From there, you powder the previously made coal or crust and, quote, add there to some fair water, about 15 fingers high, or four times as high as the powder and boil them together for one quarter of an hour. Then strain the liquor and all through a woolen cloth. That which sticks behind may be thrown away, but the liquor that passes must be taken and boiled till it come to a salt, which will be in a few hours. This recipe continues on with adding more ingredients and steeping them together until the substance became sort of a pap, which left behind a red or reddish salt after being evaporated in sand. And then that went into a retort and, quote, for the first hour began with a small fire, more the next, a greater the third and more the fourth and then continue it as high as you can for 24 hours. Sometimes by the force of fire, 12 hours proves enough for when you free the recipient white and shining with the fire. And there are no more flashes or as it were blasts of wind coming from time to time from the retort, then the work is finished. And you may with a feather gather the fire together or scrape it off with a knife where it sticks. This recipe goes on to stress the need to preserve this fire in an airtight container. And how if you put it in the sun, it might, quote, kindle gunpowder. I think that might just mean explode. This this recipe also contains a cautionary tale, quote, my author says he had once wrapped a knob in wax at handover and it being in his pocket and he busy near the fire. The very heat of it let in flame and burned all his clothes and his fingers also for though he rubbed them in the dirt nothing would quench it unless he had water. He was ill for 15 days and the skin came off. So don't do that. We should note that it's possible that paracelsis used a similar process to produce phosphorus in the 16th century more than 100 years before brand's discovery. He wrote about a process for repeatedly distilling urine, which would cause what he described as the earth air and water to rise while the fire fell out of it. After doing this several times, he said there would be quote, congealed certain icicles, which are the element of fire. That sounds close enough to what brand was doing that these icicles could have been phosphorus, but we also really don't know. It just merits mentioning as a potential comparative. Paracelsis has been on my episode list for a very long time long enough that I was getting ready to do it and then sobones did it and I didn't want to feel like I was copying sobones, even though not everybody listens to both shows. But now it's been long enough that maybe he will keep farther up the list. There are also other accounts that describe brand's process a little differently than that recipe that we just went through. And in one of them, the salts that are produced after the first round of distilling the urine are discarded, that is actually where most of the phosphorus would have been at that point in the process. So if brand was doing it that way, he would have been throwing away most of what he was trying to get. Regardless, though, this was a long, involved, complicated and frankly gross process. A 1767 dictionary of chemistry described it as more curious than useful, along with being quote, most costly and embarrassing. But brand was very fond of his costly embarrassing discovery. He named it cold fire or sometimes just my fire. It's not clear who was the first person to call it phosphorus, which is from Latin words that mean bringer of light or light bringer. That same term has also been used to describe a variety of other glowing substances. Brand kept his discovery secret for about six years. And we'll get to what happened when knowledge spread about it after we first have a little sponsor break. That big presentation for my new launch, I'm making it on Canva mobile right you suggested. I just make in everything I couldn't. So he's a bit noisy, but he's gone off. Anyways, I'm going to pin the presentation to you now. So you can see what I mean. I'm going to go on. Thanks for introducing me to Canva. Love ya! Henning Brand's discovery became public knowledge through a murky series of events involving two other men named Johann Kunkel and Johann Daniel Kraft, who like a lot of other people in the story worked in both chemistry and alchemy. It seems as though Kunkel had a piece of Bologna stone. And this was a rock that was first described in 1603 by Vincenzo Cascarolo and this stone glowed in the dark. Cascarolo was a shoemaker. Then like so many other people, he was hoping to find gold. He had collected a bunch of interesting rocks from the mountains near his home in Bologna and what is now Italy. And he discovered that if you baked them and then left them out in the sun, they would glow in the dark. Bologna stone became a curiosity and a source of fascination, as people wondered whether there was something magical about it and whether it might have something to do with the philosopher's stone. Galileo described it this way in 1612. Quote, it must be explained how it happens that the light is conceived into the stone and is given back after some time as in childbirth. Today we know that Bologna stone was in fact barium sulfide. I love how so many elements of this story are like, what if I baked some rocks? What if I distilled pee over and over? So, Kunkel was intrigued not only by Bologna stone but also by all kinds of other luminous and substances. And so when he heard that somebody in Hamburg had created something that glowed indefinitely, he got really excited. And he wrote a letter to craft about going to Hamburg to see what this was all about. In some versions of this story, Kunkel and Craft went together and Bram taught them both how to make phosphorus after craft paid him to do it. But in other versions of the story, Craft swooped in ahead of Kunkel and paid brand not only to show him how to make phosphorus, but also to keep that information from Craft. Yeah, then that version of the story Craft had to work it out for himself. And regardless of which of these as more accurate, both Kunkel and Craft did wind up knowing how to make phosphorus. Crafts started traveling around Europe with phosphorus and other glowing substances and he did experiments with them before nobles and dignitaries. This included Friedrich Wilhelm, Duke Elector of Brandenburg Prussia on April 24th of 1676. And then a year later, Craft did the same at the court of Johann Friedrich, Duke of Brunswick, Lunaburg in Hanover. Crafts friend, Gottfried Wilhelm Leibnitz, was among other things the Duke's Librarian. And Leibnitz suggested that maybe phosphorus could be used to light a whole room, but Crafts said production of that much of it would be just way too difficult. Even so, the Duke became intrigued with the idea of setting up a mass production facility out in the hearts mountains, presumably so the smell of it wouldn't bother people. Leibnitz negotiated with Brand to come to Hanover to work on the project and he recruited a workforce and started stockpiling lots of firewood and barrels full of urine. It's not 100% clear where all of this urine came from in these stories. Like there's one account that says that Brand had a relationship with a tavern keeper or a brewer or some other person who would have a clientele that peed a lot, but it's a little vague. Meanwhile, Gustav Adolf, the Duke of Mecklenburg Gustrow also heard about phosphorus and decided that he also wanted to start a phosphorus factory as well. And this Duke's representative, Johann Wachim Becher, started trying to recruit Brand away from Hanover. It seems as though Brand tried to use Becher's offer to negotiate for more money from Hanover, but he wasn't really savvy enough to do this. And instead, he just came off as kind of cranky and obstinate. And in the middle of all of this, Crafts started writing to Hanover as well, suggesting that he might actually be a better manager than Brand for this whole phosphorus production project. Leibnitz persuaded the Duke to keep working with Brand, and it appears that during all of this, Brand did finally document his methods for making phosphorus. He apparently ran a mass production facility out in the mountains for a few months. Then in the late 1670s, phosphorus and the knowledge of how to make it reached England. Robert Boyle, who was one of the founders of modern chemistry, heard about Brand's production of phosphorus from urine. And he independently worked out his own way to do the same thing about 10 years later. Boyle then worked to establish a phosphorus production facility in London. As phosphorus became more available demand for its skyrocketed. It went from being a curiosity that people thought may or may not be the philosopher's stone to something that had at least in theory practical uses. Johann Kunkel figured out how to cast phosphorus into molds underwater and wrote a treatise on the use of phosphorus in medicine called treatise of the phosphorus merabilis and its wonderful shining pills. Soon, phosphorus was being marketed as a cure-all, prepared in a variety of pills and oils and linomins. It was recommended for alcoholism, apoplexy asthma, cataracts, cholera, colic, depression, epilepsy fever, glaucoma, gout, impotence migraines, paralysis, scrofula, tetanus, toothaches, and tuberculosis. And that is only to name a few. Although phosphates have some medical uses, pure phosphorus does not treat any of these things and is in fact highly toxic and can be used as a poison. Henning Brand died around 1710. And about 30 years later, Andreas Sigismund, Margroff discovered phosphorus in edible seeds. He concluded that people were consuming phosphorus in their food and then excreting it in their urine. And this was the first step in the scientific community's understanding of phosphorus as a chemical element and of its movement through the world in the phosphorus cycle. This is a cycle that begins with phosphate rich rock and moves through water and soil into plants and animals, then back into the water and soil and then into sedimentary rock. By the early 19th century, phosphorus was seeing large-scale industrial production thanks to the discovery that it could be extracted from bone ash. Most notably, white phosphorus was used to make matches, which is something that we talked about in a prior episode on the London Match Girl strike. White phosphorus was really dangerous, though. It caused a serious medical condition known as Fossijah, and in 1849, red phosphorus was introduced as a less dangerous substitute. By 1851, phosphorus was seeing more practical uses, including in manufactured fertilizers. This actually led to a supply and demand problem, which led people to look for new sources of phosphorus. One of these was guano. Guano itself is rich in phosphates, nitrogen, and potassium, making it an excellent fertilizer. The sedimentary rocks that form in places with lots of guano are also rich in phosphates. And this led to a land grab for islands and caves with lots of guano. In 1856, U.S. Congress passed the Guano Islands Act, which allowed the United States to claim uninhabited islands to mine the guano on them. They were uninhabited by people. They were inhabited by lots and lots of birds. Today, the vast majority of phosphorus is mined from rocks that are rich in calcium phosphate, and about 90% of that mined phosphorus is put to one use, and that is back to fertilizer. Phosphorus is still used for other applications as well, including plastics, fuel additives, fireworks, rat poison, and of course, it is still used to make matches. It used to be in a lot of detergents, because like we said earlier, it helps detergents clean better, but too much phosphate and bodies of water leads to algae overgrowth, and so a lot of nations to be either banned or strictly limited the use of phosphates and detergent. Phosphorus is also used in weapons, including organophosphates, which are chemical weapons known as nerve gas, as well as incendiary devices and smoke screens. Ironically, Hamburg, where phosphorus was discovered, was hit with thousands of phosphorus containing incendiary bombs during Operation Gamora in World War Two. Yeah, the use of phosphorus and weapons is pretty controversial today, but it still is used. Phosphate rock is not a renewable resource, even though the phosphate cycle does eventually put phosphates back into rocks. It takes a really long time, and over the past few years there has been some discussion about whether the world is running out of phosphorus. Phosphorus itself is not in very short supply. It's one of the most common elements on the planet, but there's not that much of that can be mined without huge environmental damage. There's a lot of phosphorus everywhere, but only a very few places with phosphorus in a high enough concentration to be able to efficiently mine it. It's not totally clear exactly how much available phosphate there is in rocks that can reasonably be mined, or when we might reach peak phosphorus. Predictions run anywhere from decades to centuries, because the vast majority of phosphorus is used as fertilizer for plants that directly are indirectly become food. This shortage has the potential to be a global catastrophe, and one of the proposed alternatives is urine recycling. We're all the way back to just boiling some urine. The ZOX phosphorus. It's glowing and exploding. I'm glad I got this whole Hinnig brand thing out of my system after like three years of saying I should do a podcast on that guy and his weird urine boiling. Thanks so much for joining us on this Saturday. If you'd like to send us a note, our email addresses historypodcast at iHeartRadio.com. And you can subscribe to the show on the iHeartRadio app, Apple Podcasts, or wherever you listen to your favorite shows. This is an iHeart podcast. Guaranteed Human.
