Lamentations on Chemistry

The curious tale of murder by radiolysis becomes more convoluted each day. A Google search reveals an expanding table of accusations and denials, each party having some kind of axe to grind. There are the British authorities, anti-Putin exiles, Russian oligarchs, a diminishing group of fearless Russian journalists, angry and indignant ex-Soviet KGB patriots, and of course, Tsar Putin.  This case is beginning to reveal that there may be no perfectly clean parties, radiologically or otherwise. 

This is a fleeting glimse of a struggle takig place between bitter Russian ex-patriots and the Putin regime.  Some sketchy reports indicate that this disturbing battle involves an underworld of operatives working for both oligarch wise-guys and organs of the state secret police. It’s just creepy. There is no other way to put it.

But, it could easily be that the murder of Litvinenko was pulled off without the knowledge or sanction of the official security apparatus and was executed by freelancing bad guys.

Switching subjects now, a company in New Mexico called United Nuclear has an interesting commentary on it’s website, though I’m not sure that it makes any actual conclusions.  But, you can get a Polonium-210 coffee mug.  A 0.1 microCurie Po-210 source will run ya about $69.00. United Nuclear claims that their sources couldn’t have been used in the Litvinenko killing.  Assuming that their comments are accurate, I would have to agree with that conclusion.

I hasten to add that it is important that there be a commercial source of such things.  In order for people to invent new products using radiation, we need suppliers like United Nuclear.  We also need radiation sources for teachers to educate students and the public about radiation.  These people have some pretty cool stuff and it is my sincerest wish that pointy headed fools in DC do not try to clamp lots of extra constraints on to companies like United Nuclear because of the Litvinenko murder.  Gosh, it’s a good thing that Po-210 wasn’t found in somebody’s shoe. The TSA would be making us scan our feet at the airport.

So, here we go. You know the nauseating feeling and that metallic tang sensation you get on your tongue when you’ve narrowly averted a car crash or had some other close call? Well, a recent news article has left me with the same feeling.  

According to an article in the Jerusalem Post, a group of middle eastern countries have signalled to the IAEA that they are interested in establishing a “common program in the area for nuclear energy for peaceful purposes”. 

The subtext of the Israeli article is that this move is a kind of equilibration by Sunni populations in response to Iranian/Persian Shi’ite nuclear development.  The countries in question are Egypt, Morocco, Algeria, Saudi Arabia, Tunesia, and the United Arab Emirates. 

According to the IAEA, 29 nuclear reactors are under construction in the world today.  Seven of them are in India, which plans to increase their number 8-fold by 2022. China has four reactors under construction and reportedly plans a 5-fold expansion in the next 15 years.  The IAEA keeps a handy list of new and retired reactors around the world.

Here is a nuclear joke you can tell to entertain your friends! Question: How many nuclear engineers does it take to replace a lightbulb? Answer: Fifty! One to replace the bulb and forty nine to figure what to do with the old one! 

On the one hand, it is logically and morally precarious to deny others what you yourself have enjoyed since the end of WWII. That would be the reassuring hum of nuclear electricity and prospect of security through the overwhelming firepower afforded by fission. 

On the other hand, the existing nuclear states have built infrastructure for the safe movement of nuclear materials through the system and folding new states into it may not be so hard.  However, the existing nuclear states have a compelling interest in avoiding disruption of the nuclear fuel cycle. More demand means higher prices.  Maybe the existing nuclear states should form something like OPEC to regulate the supply of nuclear fuel? 

I’ll admit that I’m a bit nervous about the prospect of Middle Eastern states becoming handy in the nuclear arts.  Any given “Atoms for Peace” program could degrade into a shell game that could hide a nuclear weapons effort. 

A plain reading of history seems to show that if someone else is helping with some of the enrichment, straight fission bombs are not as hard to develop as one might have supposed. It’s hard if you start ab initio with a pitchblende mine, a cloud chamber,  and F=ma.  But if you can outsource reactors and fuel, it’s a lot easier. The art in bomb design appears to be wringing out the biggest bang for the smallest amount of fissile material. Fortunately for everyone, thermonuclear bombs seem to be substantially trickier to make- my conclusion based on the open literature. 

If you think about it, a pre-nuclear state will almost certainly conclude that not having a nuclear weapon is tantamount to suicide. So the pressure to build nuclear weapons is irresistable to many regimes.

A nuclear arms buildup among the theocratic states seems especially worrisome, even though secular states like the USSR and North Korea make a poor case for secular stewardship.  Like it or not, the notion of MAD- Mutual Assured Distruction- did provide balance in the cold war between NATO and the Warsaw Pact.  Maybe what we are seeing is a nascent MAD in the middle east.

The worst case would be where the much desired Islamic Caliphate would have a “nuclear option”.  We can only hope that islamic theocratic fever is quenched by the pragmatics of economic prosperity. This is where a levelheaded US government could lead the way.

Chins are wagging over the what is being called a slip-up by Israeli Prime Minister Ehud Olmert.  According to the New York Times, during an interview with a German cable news channel, Olmert reportedly said-

“Iran openly, explicitly and publicly threatens to wipe Israel off the map. Can you say that this is the same level, when they are aspiring to have nuclear weapons as America, France, Israel, Russia?” [Italics by Th' Gaussling]

Oops! How do you say “Faux pas” in Hebrew? 

It’s kind of silly that this is even an issue.  For quite some time the only real questions have been- 1) How many coats of Turtle Wax are on the bomb casings? And, 2) Did they buy the extended warranty?

It’s an open question as to whether or not speaking publicly about its nukes enhances their deterrent effect for Israel. Look at that fetid Stalinist shrimp, Kim Jung Il.  He waves his nuclear capability around like a brain damaged test monkey with a turd on a stick. And, of course, we afford him the courtesies alloted to a brain damaged test monkey. A’hem.

Alexander Litvinenko’s death, now deemed a murder by Scotland Yard, brings the topic of “what’s up with Russia?” right up onto the table. It’s like finding an earwig in your half eaten salad.  I gather from the tone of news articles that many are startled not just by the criminal use of a radionuclide, but by the layers of intrigue that are beginning to peel away.

Concurrent with Litvinenko’s demise, former Russian Prime Minister Yegor Gaidar suffered an event in Dublin that may have been a poisoning. His recounting of the episode in a Financial Times article is interesting. 

In some ways the transfiguration of the USSR into contemporary Russia was less of a transition from some larval stage into a butterfly than it was the color change of a chameleon. To be sure, there were substantial changes in the geopolitical tectonics. But their rigid sphere of influence is definitely smaller than in the Soviet days. 

I visited Russia not so long ago.  I had studied Russian language as an undergraduate, so I wasn’t completely helpless. Nevertheless, I had to rely on Russian speakers to help with the details of travel. Russians are like everyone else- cynical towards their own politicians, but deeply patriotic.  Truly, to know Russia is to love Russia. I love the people and the rich culture. But, in my view, to know Russia is to fear it a bit as well.

As a post-doc I sat with Soviet colleagues and watched CNN coverage of the collapse of the USSR.   We watched coverage of the rise of Yeltsin in Moscow and the failure of Scud Missiles in Gulf War I.  My friends came to the US as Soviets and returned as Russians.  It was an odd time.

So, this matter with Litvinenko is surprising but not surprising.  That this place could produce a Putin and a Gorbachev within a few years of each other is not unexpected.  What does surprise me is the low priority that the west apparently places on constructive engagement with Russia.  The west has wasted a golden opportunity following the collapse of the USSR.  

One of the interesting parts of having a blog is that you get to see the search terms that people use to find your site.  We’ve been getting lots of hits lately from persons trying to squeeze polonium information out of the web.  I went through some venerable reference books on my shelf and collated some general fun factoids on that fashionable metal - polonium.

Polonium is actually a natural element found in thorium and uranium deposits.  In the Radiation Health Handbook I count 33 isotope entries for polonium, 7 of which are metastable, or isomeric, states. The known isotopes are Po-193 through Po-218. Po-209 has the longest half-life at 103 years.   Bismuth 209 is the heaviest stable nuclide. Nuclei heavier than bismuth often emit alpha particles, and do so exothermically or spontaneously.  Polonium, one atomic number above Bi, has no stable isotope. 

Loss of an alpha particle results in a drop of atomic weight of 4 and atomic number of 2.  You can think of an alpha particle, or helium nucleus, as a good leaving group.

Polonium is very scarce.  Its discovery, well known for being famous, was by Marie Curie and was accomplished by isolation from tons of ore. It was named after her home country of Poland. Today the the production of Po is effectively limited to Po-210  and is bred in nuclear reactiors via the transmutation of Bi-209 by neutron absorption to afford Bi-210.  Neutron rich nuclides can drop their neutron count through the emission of beta particles (electrons) with a subsequent uptick of atomic number by one. So the Bi-210 nucleus transforms to Po-210 by beta emission.  The polonium is isolated by fractional distillation from the remaining bismuth.

One gram of pure Po-210 is said to evolve 141 watts of heat. Consequently, one use of Po-210 has been for thermal electric power generation. It’s near exclusive emission of alpha’s minimizes shielding problems.  Another important use of alpha emitters is for the generation of neutrons. This interesting process uses alpha particles to interact with beryllium nuclei to afford the extrusion of neutrons.  In this way it is possible to have a compact neutron source.  Place the source in a tank of water or paraffin, arrange for an opening, and presto! You have a cheap neutron beam source- sometimes called a neutron Howitzer.  Plutonium-beryllium (PuBe) is more common than polonium because of the long half-life of available non-fissile plutonium sources. The neutron Howitzer is commonly used in neutron activation studies.

The chemistry of polonium is exotic by virtue of it rarity and the pragmatics relating to its high specific activity.  It’s high specific activity causes it to radiolyze the solvent that the reaction or other manipulation is occuring in.  This is especially problematic for organic solvents. The high activity will pose serious safety risks for the chemist in handling. Advances in organopolonium chemistry have been complicated by the pyrolysis of the organic fragments via radiolysis.  This also complicates the preparation of crystals for x-ray crystallography. A properly equipped facility night have a remote manipulation setup for handling high activity materials.  This is especially critical when the permissable body burdens are in the picogram range. 

I keep thinking about this Alexander Litvinenko character who, as the media reports, was mortally radiolyzed.  Irrespective of the intent of the bad guys, the effect of it may go far beyond the mans unfortunate death.  It is a kind of vignetted picture of what terror with radioactive materials might look like. 

In a quiet location, a lab perhaps, or a public storage shed, the bad guys had to formulate some kind of potion, some kind of concentrate that could be added to Litvinenko’s food or drink without alerting him to the change.  And I think it is reasonable to assume that the perpetrators are not “suicide poisoners”, so they would have to do the deed without contaminating themselves. So either the poison was prepared in the field by the perpetrators, or it was prepared in advance by others elsewhere.  It might even be that the person(s) who administrated the poison were unaware that it was a radiological hazard.

Because Po-210 only emits alpha’s, in principle a hermetically sealed container with a small quantity could be moved past radiation detectors at ports of entry without triggering alarms made to detect gamma radiation. This assumes that the polonium is highly pure. Trace contaminants that are gamma emitters could be detectable.  And because Po-210  as the pure nuclide is a strict alpha emitter, it’s shielding requirements would be minimal.  This nuclide seems well suited for villany.   

On the plus side to this scary scenario is the short half-life of Po-210.  Admittedy, this offers scant comfort for those who might ingest or inhale the material.  But, by comparison with gamma radiation where heavy shielding and/or a goodly distance from the source is needed, the short half-life of Po-210 and the poor penetrating ability of alpha particles makes remediation a little easier, at least in principle.  Inhalation and ingestion are the main exposure problems with alpha emitters.

It will be interesting to see if the Chicken Littles in congress will rush back to the hen house extrapolating furiously (flapping and clucking noises) about this “new threat” to homeland security.  Lordy.   Let’s hope they don’t screw up things too badly for legitimate users of radioactive materials.

It is hard to say just how widespread radiological crimes could become.  Because of the short 138 day half-life of Po-210, an accumulated stockpile would rapidly dilute with Pb-206. This event may result in a tightening of the supply of such materials.  My guess is that terrorists will look to other rad materials for their maleavolent designs. The Litvinenko murder has the appearance of an assasination by an organization that actually has a mailing address.