Pod Insights Stuff You Missed in History Class SYMHC Classics: Hennig Brand About this episode This 2019 episode shares how Hennig Brand discovered phosphorous by boiling pee. But he was really thought the secret to the philosopher’s stone might be found in urine.
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2:18 Tracy V. Wilson? Happy Saturday. This week, we talked about rickets and vitamin D. And we mentioned that in 1669, Hennig 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.
2:39 Holly Frey? At the beginning of this classic, we talk about an event called BaFest. 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.
2:51 Tracy V. Wilson? So enjoy.
2:55 Holly Frey? Welcome to Stuff You Missed in History Class, a production of iHeartRadio.
3:05 Tracy V. Wilson? Hello and welcome to the podcast. I'm Tracy V. Wilson.
3:09 Holly Frey? And I'm Holly Frey.
3:10 Tracy V. Wilson? Every year, there's a thing in Cambridge, Massachusetts called BaFest. 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.
3:54 Tracy V. Wilson? 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 Hennig Brand Discovering Phosphorus. Hennig Brand discovered phosphorus by boiling pee. So the first time I heard about this at BaFest, I was like, we gotta 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. Hooray.
4:44 Holly Frey? I love a pee joke. They're very funny to me because I'm crass.
4:48 Tracy V. Wilson? One of my cousins has a daughter who's just at the age to be having sleepovers and and at the age where mentioning of any bodily function is just instantly hilarious. And I like remember as a kid, if somebody was like pee pee, it would just send everyone into giggles forever.
5:06 Holly Frey? 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 produce. 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, no.
5:27 Tracy V. Wilson? It's a very different culture.
5:29 Holly Frey? Yeah, yeah, yeah, yeah. A little Victorian in my house in that regard.
5:34 Holly Frey? To the matter at hand, phosphorus is a chemical element. And if you need a quick chemistry refresher, elements are a basic building block of matter. And the 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.
6:02 Tracy V. Wilson? Yeah.
6:03 Holly Frey? I'll take one phosphorus, please.
6:07 Tracy V. Wilson? 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.
6:48 Holly Frey? Phosphorus, on the other hand, is the first element whose discoverer we can name, and that was Hennig 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 white or yellow phosphorus. White phosphorus can then be used to make more stable alatropes, 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.
7:30 Tracy V. Wilson? 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.
7:53 Holly Frey? 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 time 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.
8:38 Tracy V. Wilson? 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.
9:20 Tracy V. Wilson? 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 any sort of household cleaning tip.
9:47 Tracy V. Wilson? When we were in San Francisco at the end of our tour last year, I went to the Bookbinders Museum, and I had a guided tour of the Bookbinders Museum. And one of the things that I learned about is how in one element or one part of the bookbinding printing process, there were these little ink daubers that were sort of leather-covered things that you would daub in the ink, and you would put that on the plate that you were going to print. And if that dried out, your apprentice had to go and clean them and start completely over. So part of the apprentice's job was to keep that nice and moist. And the tour guide said, "Do you have any ideas of what they might have used to clean these things?"
10:29 Tracy V. Wilson? And I was like, "I bet it's urine," because that was the thing that I could think of that would be, you know, in the early days of bookbinding, would probably use to be cleaned, to clean something. And she specified that it was stale urine, and that is for the reason that we just said. So, of course, when Henegbrand 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.
11:13 Tracy V. Wilson? 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. 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 Hennig Brand, 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 and prolong life. And Brand was one of them. Hennig Brand's discovery of phosphorus came about because he thought the secret to the philosopher's stone might be found in urine.
11:56 Tracy V. Wilson? And we'll get to why he thought that and how he made his discovery after a sponsor break.
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12:55 Speaker 06 It was going to rival anything that was already built. And that takes quite a bit of people and different teams to all be on the same page.
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15:40 Tracy V. Wilson? We do not know all that much about Henning Brand as a person. Sometimes his name is spelled Henning instead of Henning. 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 in what's now Germany sometime around 1630. He seems to have spent some time as a low level army officer during the Thirty 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.
16:17 Holly Frey? 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.
16:40 Tracy V. Wilson? After Brand's first wife died, he remarried a woman named Margareta, 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."
17:04 Holly Frey? As we said before the break, Brand was looking for the philosopher's stone, which was believed to turn base metals 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.
17:27 Tracy V. Wilson? 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 its use as 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 saltpeter, and then the saltpeter 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
18:07 Tracy V. Wilson? 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 urabylan, which is one of the end products of the bodies breaking down the iron-containing molecule heme.
18:27 Holly Frey? Brand's 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.
18:44 Tracy V. Wilson? One day, as Brand was distilling urine in 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.
19:03 Holly Frey? I'm sorry to laugh.
19:06 Tracy V. Wilson? It is funny, though.
19:09 Holly Frey? It's like, my fiery garlic glowy. 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 whitish, waxy substance that was very volatile if exposed to air, and it had a bluish 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 Hooke, which was published in London in 1726.
19:43 Holly Frey? 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 all was involved in this.
19:56 Tracy V. Wilson? So, under the heading Phosphorus elementaris by Dr. Brandt of Hamburg, it reads, quote, "Take a quantity of urine, not less for one experiment than 50 or 60 pails full. Let it lie steeping in one or more tubs or an hog's head of oak and wood, till it putrefy 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,
20:37 Tracy V. Wilson? 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."
20:46 Holly Frey? So, for one batch of phosphorus, Brandt was leaving urine out in pails 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."
21:25 Tracy V. Wilson? 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, begin 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..." 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.
22:10 Holly Frey? 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."
22:20 Tracy V. Wilson? I think that might just mean explode. This recipe also contains a cautionary tale. Quote, "My author says he had once wrapped a knob in wax at Hanover, 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."
22:51 Holly Frey? So don't do that. We should note that it's possible that Paracelsus 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.
23:31 Tracy V. Wilson? Paracelsus has been on my episode list for a very long time, long enough that I was getting ready to do it, and then Sawbones did it, and I didn't want to feel like I was copying Sawbones, even though not everybody listens to both shows. But now it's been long enough that maybe he will creep 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.
24:11 Holly Frey? 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, "both costly and embarrassing."
24:26 Tracy V. Wilson? 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.
24:49 Holly Frey? 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.
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28:13 Tracy V. Wilson? Hennig 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 this 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.
28:39 Holly Frey? Cascarolo was a shoemaker, and 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, in 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.
29:20 Tracy V. Wilson? 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 luminescent 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 Kraft about going to Hamburg to see what this was all about.
29:47 Holly Frey? In some versions of this story, Kunkel and Kraft went together, and Brand taught them both how to make phosphorus after Kraft paid him to do it. But in other versions of the story, Kraft swooped in ahead of Kunkel and paid Brand not only to show him how to make phosphorus, but also to keep that information from Kraft.
30:05 Tracy V. Wilson? Yeah, in that version of the story, Kraft had to work it out for himself. And regardless of which of these is more accurate, both Kunkel and Kraft did wind up knowing how to make phosphorus. Kraft 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 24 of 1676. And then a year later, Kraft did the same at the court of Johann Friedrich, Duke of Brunswick-Lunenburg in Hannover.
30:38 Holly Frey? Kraft's 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 Kraft 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 Harts 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.
31:13 Tracy V. Wilson? 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 deuce representative, Johann Joachim Betzer, started trying to recruit Brand away from Hanover.
31:52 Holly Frey? It seems as though Brand tried to use Betzer'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, Kraft 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.
32:22 Tracy V. Wilson? 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.
32:51 Holly Frey? As phosphorus became more available, demand for it 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 Mirabilis and Its Wonderful Shining Pills. Soon, phosphorus was being marketed as a cure-all, prepared in a variety of pills and oils and liniments. It was recommended for alcoholism, apoplexy, asthma, cataracts, cholera, colic, depression, epilepsy, fever, glaucoma, gout, impotence, migraines, paralysis, scrofula, tetanus,
33:33 Holly Frey? toothaches, and tuberculosis, and that is only to name a few.
33:37 Tracy V. Wilson? 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.
33:45 Holly Frey? Henning Brand died around 1710. And about 30 years later, Andreas Sigismund Margraf 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.
34:19 Tracy V. Wilson? 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 Girls' strike. White phosphorus was really dangerous, though. It caused a serious medical condition known as phosyjaw, and in 1849, red phosphorus was introduced as a less dangerous substitute.
34:47 Holly Frey? 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, US Congress passed the Guano Islands Act, which allowed the United States to claim uninhabited islands to mine the guano on them.
35:27 Tracy V. Wilson? 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 in bodies of water leads to algae overgrowth, and so a lot of nations have either banned or strictly limited the use of phosphates in detergent.
36:09 Holly Frey? 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 Gomorrah in World War II.
36:28 Tracy V. Wilson? Yeah, the use of phosphorus in 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 it that can be mined without huge environmental damage. Like, 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.
37:12 Holly Frey? 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 or indirectly become food, this shortage has the potential to be a global catastrophe. And one of the proposed alternatives is urine recycling.
37:38 Tracy V. Wilson? Or all the way back to just boiling some urine until
37:43 Holly Frey? The DIY phosphorus method.
37:45 Tracy V. Wilson? It becomes glowing and exploding.
37:49 Tracy V. Wilson? I'm glad I got this whole Hennig 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.
38:03 Tracy V. Wilson? Thanks so much for joining us on this Saturday. If you'd like to send us a note, our email address is [email protected] . And you can subscribe to the show on the iHeartRadio app, Apple Podcasts, or wherever you listen to your favorite shows.
38:24 Holly Frey? A rare disease diagnosis can change your life, but it doesn't have to define your future. In season seven of Untold Stories: Life with a Severe Autoimmune Condition, host Martine Hackett continues the conversation with people living with MG, CIDP, and the broader rare disease community, exploring what comes after diagnosis through stories of hope, progress, and connection. Produced by Ruby Studio in partnership with Argenx. Listen on the iHeartRadio app, Apple Podcasts, or wherever you get your podcasts.
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