Burning Cuyahoga: A Technical Appendix to Postblogging Technology, June 1956

 

I've got one word for you, son: Organophosphates. 

The Wiki entry on the Cuyahoga River of northeastern Ohio is actually pretty interesting. The word seems to be Seneca. The river isn't long, but  is important, running through the major Ohio city of Cleveland. It appears to have been the western border of the Haudenosaunee, but local archaeologists and historians are having difficulty sorting out the pre-contact ethnology of the Whittlesay cultural horizon, which might be Fort Ancient, which I think is thought to have been Siouan, but also Algonquin-speaking and associated with the Monongahela horizon, which is thought to have ben Iroquoian. Historically both Ottawa and Wyandot (Huron)  communities are know, which for me raises the question of early Catholic parochial activity in the region. We're told that it isn't surprising that the attested first Catholic church in Cleveland, St. Mary's-on-the-Flats, has no history prior to 1878, even though the Diocese of Cincinnati was erected in 1821, well before the beginning of significant Irish Catholic emigration, a bit of an issue in its own right, and the parish had a resident pastor from 1835, with St. Mary's being dedicated on 7 June 1840 by a visiting French bishop, who seems to have made something of a revivalist tour through Catholic, and especially French Catholic America. So in other words the early Catholics of Cleveland were probably Metis rather than more respectable Irish Catholics and that's probably why the early colonial history of the region is so obscure. 

The same can't be said for the Cuyahoga Fire of 22 June 1969, which turns out to be No Big Deal in the long history of at least thirteen Cuyahoga river fires, but a very big deal and watershed (did you see what I did there? Because I did it!) in American environmental history. Or at least that's the impression the Wiki gives. It's the sheer density of industrial development along the river, rather than any particularly egregious polluter, that accounts for the frequent fires. And, notwithstanding the subject of this week's post, it was bog standard POL surface slicks that caught fire and not sudsing organophosphate artificial detergents, such as are responsible for the "foaming rivers" of Jolly Old England going back to the Fifties. Honestly, when I opened the "Cuyahoga River" article I was expecting to hear something about mass market U.S. laundry detergents, foaming rivers, and eutrophication, not oil slicks catching fire. I was especially not expecting to hear about rhetorical links with narratives of decaying urban centres and, sigh, structural racism. Whatever you might think about burning rivers, it turns out to have been a strong driver of White Flight. 

Which is kind of too bad, because there's a lot of  hinky stuff going on with organophosphates!

While you're asking him about the Ark of the
Covenant, can you talk to Dr. Jones about
site preservation and find documentation?

 To get this out of the way, organophosphates are when a phosphate molecule (O=P(OR)_{3) binds to an alkyl or aromatic, which happens all the time when you put yucky living stuff in with phosphoric acid, which is ubiquitous, and good thing, too, because DNA, RNA, and ATP are all organophosphates. It turns out that the phosphate molecule is a lot more chemically active than it has a right to be, hypervalently forming more bonds than the octet rule allows,  for reasons which are the subject of active research in the field of computational chemistry, which we apparently need to understand things way instead of just twisting our molecule models around and talking about "d" and "p" orbitals. Is it negative hyperconjugation? Something more complicated? No wonder that Gerhard Schrader, a chemist working for I.G. Farben, was beavering away at organophosphate compounds in the Germany of the 1930s! (Yay! The Neue Deutsche  Biographie is online now!)}

_{Dr. Schrader's Wikipedia entry is very succinct and does not have a picture, but Google Image comes through, as it turns out the nice biographer at Wikipedia wasn't trying very hard. It's almost like the guy who invented nerve gas and gave it to the Wehrmacht for WWII is famous or something. "Notorious?" I mean, it's not like the Nazis did anything bad with nerve gas or anything. Why, the gas they used at Auschwitz was an insecticide. Wait. Dr. Schrader worked on insecticides, too? And it was obvious from the first that the mechanism of lethality made it dangerous to humans, too?} 

In the future, humans are using insecticides to kill all insects, so emergent Gaia
sets them right. One of the villains is a Red Chinese scientist conealing the fact
that the successful Chinese effort h as led to the sterilisation of the country, whihc,
of course, totalitarian dictatorships can easily conceal. 

_{Hmm. Maybe Dr. Schrader should work on not being recognised on the street. Fortunately, NDB tells us, after he patented Demeton ("Systox") in 1951, he had the money to be obscure. some kind of notorious figure, and remind everyone that all he ever wanted to do was prevent world hunger. By eliminating all the "life unworthy of life." No, don't look at me like that! I mean insects.}

It's a funny road we take. The organophosphate insecticides are all quite dangerous, and although they were widely used as early as the Fifties, their real  heyday began after we decided that DDT was worse. Which, not to defend DDT, it was due to bioaccumulation. 

Meanwhile, the postwar era saw a boom in interest in Nazi war gasses. The US Chemical Corps began experimenting with VX, which, it says here, emerged from ICI work on pesticides in 1952. Wikipedia says that Schrader's research was the basis of the work, but someone's got shirty about it at Wiki and asked for a citation. I'd hate to think that German engineering superiority led to a nerve gas research gap! Anyway, ICI's new insecticide, Amiton, was soon noticed to be incredibly lethal, so some scienticians carried the work off to Porton Down, where, an unfortunate lab death aside, its advantages as an "area denial weapon" were soon realised. The US produced 4400t of the stuff during the Cold War, while the Russians got their similar VR ("Now with more Marxism") production up to 15,500t. The first VX weapons deployed by the US Army were actually designed for sarin, which is made by a process which leaves considerable HCl in the final product, making it corrosive to containers and short-lived, leading to much experimentation with buffering and binary deployment. Anyway, everyone decided that the stuff was more work than it was worth, except the FSB, and the thought is that they use that stuff to make a point, more than anything else. 

So, anyway, lots of fun for chemists, and to think it all started with soap! This means mostly Sodium triphosphate, a miracle chemical that improves detergent surfactant action in hard water and has a variety of other uses that we begin to appreciate after having the phosphate bond's extraordinary chemistry brought to our attention, if not understanding. As the name implies, this is just a salt of polyphosphate, and you might expect it to appear in any brine where there are polyphosphates present, which takes us back to the work of "L. Liberman," who is one of those early scientific workers with a highly contingent immortality based on citation in the works of another, which is why we don't even know his first name. (Look, I'm sure someone could track it down, possibly on the Internet, but it didn't turn up in my search, and I'm tired from making Wiley Online display the first page of the citing paper, Readman [1890]. Wikipedia says that at first chemists thought that the molecule, which only forms in extreme conditions, they thought, was some kind of fossil, like dinosaur bones; but then they found that there was an organic synthesis and that it was important in biology, and at some point they started making it as a stabiliser for nitrocellulose products and then as a flame retardant, and eventually as a desert topping and a floor wax. (Sometimes it turns out that the joke wrote itself, these many years ago.)

 

I dunno. Seems like the phosphate's main crime all along has been hanging around with human beings. That, and eutrophication. And giving rivers a foaming head when too much of it is in the factory wastewater. It's interesting to stumble across a fundamental, unsolved problem in chemistry. I thought chemistry didn't have that kind of thing! 

_{Also, do they ever say "Great Ooze," for "Great Ouse," over there in Jolly Old England? It seems like a low-hanging fruit, but maybe Up North "Ouse" is a three-syllable word.}