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JohnWW
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Thallium poisoning
Has anyone here been following the case in the news of poisoning of the former Russian spy, Colonel Alexander Litvenenko, who defected from the KGB
and fled to London, England, and gained political asylum, after publicly disagreeing with the Russian president, Comrade Vladimir Putin?
About 11 days ago, he was invited to a sushi restaurant in London by a mysterious contact who claimed to have information on who may have killed a
Russian woman journalist who was an outspoken critic of Putin several months ago, which murder Litvenenko was investigating. Papers naming names were
shown or passed to him. Several hours later, he was admitted to hospital complaining of stomach pains, and his condition rapidly deteriorated and he
was sent into intensive care and isolation from infection, where he is under armed security police guard. MI6 and the police anti-terrorism squad are
investigating.
His principal symptoms included all his hair falling out, a pale appearance, and drastically lowered white blood cell count. This, and preliminary
tests, led to a diagnosis of thallium poisoning, suggesting that he had been given what should have been a lethal dose of about 1 gram of a soluble
thallium salt. However, final tests are yet forthcoming. Further symptoms suggest that he may have been poisoned by something else as well, including
a radioisotope, which may have been a radioactive thallium isotope, and that he will need a bone-marrow transplant in order to recover.
While attracting wide news coverage in the west, the case has gone almost totally unreported in the government-controlled major media, except for one
or two small independent radio and TV stations. This, and the obvious reason for Litvenenko's poisoning, strongly suggest that the KGB was behind it,
although they have denied it as usual.
Does anyone know much about thallium poisoning? It was used in an Agatha Christie novel, "The Pale Horse". The whole case reads like a James Bond
novel - I am rather surprised that Ian Fleming did not write one about James Bond investigating the poisoning of a KGB defector.
Thallium is most stable in the Tl(I) oxidation state, which rather resembles Ag(I), while the Tl(III) state is moderately oxidizing. Highly
water-soluble salts, which could have been slipped into coffee served to Litvenenko, include Tl(I) nitrate, fluoride, and acetate, and Tl(III)
chloride. Of these, Tl(I) acetate is the most nearly tasteless and one of the most soluble, and most likely to be used to poison someone in food or
drink; it has a S.G. of 3.68, and is so soluble in water that it is used as the basis of "Clerici's solution", with a S.G. of about 2.7, which is used
analytically to separate heavy particles in fine powder mixtures from quartz or similar light rock mineral particles.
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12AX7
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Just who determined the taste of thallium salts? 
Tim
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BromicAcid
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There was a famous case in America where a whole family was poisoned by their neighbor. They used a thallium based rat poison and put it in their
coca-cola. No one figured it out till their illness was fairly progressed. As I understand it there are some therapies out there now for treating
thallium poisoning.
I also have a book on poisoning methods and it lists thallium poisoning as one of the most horrible ways to die and goes through a number of the
symptoms both physically and psychologically a victim would experience.
It's amazing how few people know anything about the toxicological properties of thallium compounds. Arsenic seems to hold top roost, you can almost
never find arsenic salts or metal on eBay, but antimony, which is, as I understand it, similarly toxic, is available most of the time for $10 a pound
or so.
There was a book written on the aforementioned thallium poisoning called Poison Mind, the link to the amazon book is:
http://www.amazon.com/Poison-Mind-Murderer-Policewoman-Justi...
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pantone159
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Tl(I) replaces K in the body machinery, as it fits in those places, but it doesn't work right, so those systems quit working.
Supposedly, Prussian blue (potassium ferric ferrocyanide) acts as an antidote if taken right away, the Tl(I) works its way into the Prussian blue
structure, and since that is insoluble, it gets removed. The same trick works to remove Cs, which is important in the case of the radioisotope
Cs-137.
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Ozone
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Hello,
I have been following this with interest. This KGB fellow is included with at least 2 (maybe 3) journalists who have *obviously* been assassinated.
Although the toxidrome for thallium is well known (but, often expresses somewhat differently in various patients), the mechanisms behind its toxicity
are unknown.
What is known, is that the element binds to melanin in skin and hair follicles, and that alopecia is ubiquitous as a result of arrested mitosis (whew,
*bad*). So, radiothallium is not expressly required for this symptom.
There is much information here:
http://www.inchem.org/documents/ehc/ehc/ehc182.htm
Also be sure to check out:
Casarett & Doulls The Basic Science of Poisons
and,
Gonzales, T.A., Vance, M. and Helpern (1940), Legal Medicine and Toxicology., pp. 513. (My copy is *well loved* and I have thought of scanning it for
the archives; it's a classic).
Besides arresting mitotic division, I suspect a disruption of protein synthesis as well. Otherwise, it resembles Pb, in terms of generalized
heavy-metal toxicity (a virulent one at that, 0.2-0.5g LD). Thallium also appears to be nephrotoxic as well (see Cd), a paper is attached here; see
pp. 16 (I was lazy and did not excise this bit and re-distill it).
The trick is, how was it administered? My guess is with the drink; I think the food at a sushi joint would require too much conspiracy.
You are what you eat,
O3
Attachment: Thallium pp 16.pdf (623kB)
This file has been downloaded 917 times
-Anyone who never made a mistake never tried anything new.
--Albert Einstein
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The_Davster
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Heard a story from an old professor of mine, a grad student was working with Tl salts over an extended period of time, no special protection nor
accidental exposure(that was mentioned). A while later he developed gray sores on his body which doctors did not have any idea what they were. Until
they analysed them chemically...it was thallium metal being deposited on his skin.
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unionised
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There was a case of some bloke (Graham Young) who poisoned a number of his family with Tl. He was young at the time so he was locked up for a while
but the records were wiped clean when he was released from psychiatric care. He then went on to get a job in a photograhphic lens makers- one of the
few places where Tl is legitimately used and (old habits die hard) he went on to poison a number of his workmates.
He got caught when he mentioned to the people investigating this outbreak of "illness" at his workplace that the symptoms looked like Tl poisoning.
Someone got suspiciuos of how he knew so much about it.
He was found guilty and imprisoned but not for long. He died "mysteriously" in prison.
There's a film about his life "A young poisoner's handbook" for those who are interested and he also gets a good write up in John Emsley's interesting
book "the elements of murder".
Much more to the point, Tl is named after the Greek word for a green shoot because it gives a nice clear green colour in a flame test.
If " the Authorities" can't find Thalium in a poisoning case they need to get someone more competent. If it's a radioisotope then (unless it's a
really short half-life one) then they really need shooting- don't they know you can get a geiger counter on Ebay?
My money is on this being a rather more esoteric poison.
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chemoleo
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How about selenium?
It also makes your hair fall out, and produces similar symptoms.
Surely though the meds must have thought of it.
The more I am VERY surprised they didnt figure out what the poison was, given all the analytical methods available.
Poor fellow. What a way to go. This KGB 1960s shit is so outdated it hurts.
Never Stop to Begin, and Never Begin to Stop...
Tolerance is good. But not with the intolerant! (Wilhelm Busch)
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JohnWW
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I have just heard on the radio and TV news that Col. Alexander Litvenenko has just died, in intensive care at the University Hospital, London.
Apparently, the pathologists now think that he was poisoned with either something else other than thallium but which caused similar symptoms, or with
something besides thallium. An anti-cancer drug has now been suggested, along with a radioisotope. However, it will be some weeks, probably, before
analytical tests for all possible substances have been completed. It will take a real-life James Bond to crack this case.
[Edited on 24-11-2006 by JohnWW]
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Jdurg
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| Quote: | Originally posted by chemoleo
How about selenium?
It also makes your hair fall out, and produces similar symptoms.
Surely though the meds must have thought of it.
The more I am VERY surprised they didnt figure out what the poison was, given all the analytical methods available.
Poor fellow. What a way to go. This KGB 1960s shit is so outdated it hurts. |
I don't think there are any selenium compounds out there which you could easily spike someone's food or drink with and not have them know about it.
Selenium compounds REEK!
\"A real fart is beefy, has a density greater than or equal to the air surrounding it, consists of the unmistakable scent of broccoli, and usually
requires wiping afterwards.\"
http://maddox.xmission.com. |
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chemoleo
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But SeO2 doesnt. Nor does red amorphous Se.
From wiki
| Quote: | | Symptoms of selenosis include a garlic odour on the breath, gastrointestinal disorders, hair loss, sloughing of nails, fatigue, irritability and
neurological damage. Extreme cases of selenosis can result in cirrhosis of the liver, pulmonary edema and death |
I suppose they'd have noticed the garlic breath though....
[Edited on 24-11-2006 by chemoleo]
Never Stop to Begin, and Never Begin to Stop...
Tolerance is good. But not with the intolerant! (Wilhelm Busch)
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YT2095
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turns out it wasn`t Thallium but Po210 that poisoned him.
\"In a world full of wonders mankind has managed to invent boredom\" - Death
Twinkies don\'t have a shelf life. They have a half-life! -Caine (a friend of mine)
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Jdurg
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| Quote: | Originally posted by chemoleo
But SeO2 doesnt. Nor does red amorphous Se.
From wiki
| Quote: | | Symptoms of selenosis include a garlic odour on the breath, gastrointestinal disorders, hair loss, sloughing of nails, fatigue, irritability and
neurological damage. Extreme cases of selenosis can result in cirrhosis of the liver, pulmonary edema and death |
I suppose they'd have noticed the garlic breath though....
[Edited on 24-11-2006 by chemoleo] |
Yes, but you couldn't spike someone's food with that stuff and not have it be noticeable. Red selenium morphs right back into gray/black selenium as
soon as ANY type of heat source is put near it. In addition, it is a very noticeable and very bright red compound. SeO2 will also react with many of
the compounds commonly found in food and give off a very noticeable stench. Yes, it is possible to poison someone with selenium but the person would
need to have no sense of smell and incredibly poor vision.
\"A real fart is beefy, has a density greater than or equal to the air surrounding it, consists of the unmistakable scent of broccoli, and usually
requires wiping afterwards.\"
http://maddox.xmission.com. |
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Biginelli
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Thallium is quite possible for another reason: there was an analogous case 25 years before, namely the poisoning of DDR citizen Wolfgang Welsch in
1981 (for writing a memorandum against accepting DDR into UN) by Stasi agents. Thallium was used in that case; more of all, this was corroborated by
medical analysis. This was the only case against such an action brought in the court in mid-90s.
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JohnWW
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I have seen on the internet news, and heard on the radio news, that it was not Tl, or even radioactive Tl-201 (its stable isotopes are 203 and 205),
that killed him (unless it was as a minor component of the dose given him), but radioactive polonium-210. Po-210 can be made by bombarding stable
Bi-209 (the heaviest completely stable isotope known) with neutrons (from a Ra-Be source, probably), which converts it to unstable Bi-210, which in
turn quickly emits a beta-particle to become Po-210. It is the most easily obtained isotope of Po. See http://www.answers.com/topic/polonium and http://www.ead.anl.gov/pub/doc/polonium.pdf and http://library.thinkquest.org/10676/Period/po.html and http://www.chemicalelements.com/elements/po.html . Polonium has no stable isotopes, and its longest-lived one, Po-209, has a half-life of only
102 years (decaying mostly by emitting a gamma and K-electron capture to become Bi-209, and partly by emitting a neutron and then K-electron capture
to become Pb-208). Po-210 is an alpha-emitter with a half-life of only 138.39 days, decaying to stable Pb-206, one of the four stable isotopes of Pb.
Apparently, Col. Litvenenko's urine was found to have substantial alpha-particle radiation having the energy characteristic of those from Po-210.
Confirmation could presumably come by chemically analysing for Po, e.g. by atomic absorption spectroscopy. The stuff, in the form of a soluble Po
compound, must have been "slipped" into tea or other drink served to him while he visited a London hotel with two mysterious Russians on 1st November,
probably while his attention was distracted by documents being shown to him. Later that day, he visited a London sushi restaurant with an Italian
researcher into state-sponsored terrorism, who is almost certainly innocent, and it was only after that he began feeling ill.
The most easily-obtainable oxidation state of Po is (IV), with the (VI) state being either unattainable or very strongly oxidizing (like
bismuthate(V)). The most likely soluble compound used to poison him would have been sodium polonite, Na2PoO3, possibly administered in a mixture with
the selenite or tellurite, and possibly along with thallous acetate. Po(IV) would be not only chemically highly toxic like compounds of Te(IV) and
Se(IV), being similarly degraded in the liver (Litvenenko's liver was effectively destroyed, hence his jaundice) to compounds like H2Po, Po(CH3)4, and
Po(CH3)2 (these would be very smelly!), but also radioactively toxic, hence the destruction of his bone-marrow cells. In a country like Russia, ONLY a
technological government agency like the KGB would have access to Po-210, which means that Putin's denials of KGB involvement are lies, unless it were
a "rogue element" in the KGB.
[Edited on 25-11-2006 by JohnWW]
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MargaretThatcher
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I think the radiological toxicity of Po210 far outweighs the chemical toxicity. It would be pointless co-administering a gramme or so of thallium
compound with such a toxic substance.
The reformative effect of punishment is a belief that dies hard, I think, because it is so satisfying to our sadistic impulses. - Bertrand Russell
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nitro-genes
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What I don't understand is the nature of the toxin used. It is certainly no low profile toxin and can easily be traced, as they in fact did. There are
a lot of toxins that are almost undetectable and can be fatal weeks or even years after exposure. In other words, what happened to the classy
ricin-firing-umbrella?! 
Poor basterds, even the KGB has probably no money anymore to function properly....
[Edited on 25-11-2006 by nitro-genes]
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The_Davster
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I doubt tracing stuff over there is as easy as here. It could have been some sort of industrial waste; why buy poisons when people will give you
waste that is just as nasty for free...
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MargaretThatcher
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On the contrary, Po-210 is a product of nuclear research reactors - very expensive and difficult to procure. Its very nature means that the source is
no mystery. If they could get to the guy and administer such an awkward compound, they could more easily have stuck cyanide in his tea, or ricin or
whatever. I think this is a very public way of setting an example.
The reformative effect of punishment is a belief that dies hard, I think, because it is so satisfying to our sadistic impulses. - Bertrand Russell
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unionised
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"In a country like Russia, ONLY a technological government agency like the KGB would have access to Po-210, which means that Putin's denials of KGB
involvement are lies, unless it were a "rogue element" in the KGB."
What relevance has the availabillity of Po in Russia?
It's perfectly possible that he was poisoned by someone who wanted to discredit Putin's government. The CIA or MI6 would be perfectly capable of
getting hold of Po. I'm not saying that's likely- just that, as scientists, we shouldn't jump to conclusions.
(BTW, Bi has no stable isotope 209Bi has a very long half life.)
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JohnWW
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Besides making the stuff in a secret nuclear laboratory in Moscow as described above, the KGB would have had to somehow smuggle the freshly-made
Po-210 (half-life only 138 days) into the U.K.. Its strong radioactivity would have shown up as an anomaly on the X-ray screen in the form of a bright
halo, if it had come into London in ordinary air passengers' baggage, all of which is now X-rayed, and any chemical poisons brought with it may also
have suspiciously fluoresced under X-rays (as do also many drugs such as cocaine and heroin, and many explosives). The Po-210 and any chemical poisons
must, therefore, have been somehow smuggled in by the KGB other than through ordinary passengers' baggage, mostly likely in diplomatic baggage which
is immune to search, and quite possibly on board a special diplomatic plane, being thereby delivered into the hands of the KGB attache in the Russian
Embassy.
The latest I have heard is that the British Government, not believing Putin's denials of KGB involvement, has summoned the Russian Ambassador and
demanded an explanation. The whole case has the "fingerprints" of the KGB all over it.
Unionized: As for motives to kill Col. Litvenenko, only Putin and the KGB would have had any conceivable motives, i.e. revenge and to prevent the
disclosure of any further damaging information, because of the Colonel's constant published severe criticisms of them, in which incriminating facts
about them had been disclosed. The CIA and MI5 or MI6 would have been quite content to sit back and "lap up" his revelations, as he was effectively
(if not formally) working for them.
[Edited on 25-11-2006 by JohnWW]
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Ozone
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Well...
Either the 210 Po is in fact rather clever *or* a red herring. 210Po would have the advantage of being very toxic while transmuting rather quickly
into 206 Pb, which is a stable isotope (%abun. ~24%). This would make the doses small, and very hard to trace (unless you look for 206Pb exceeding the
normal isotopic abundance using ICP/MS-you would need to ash Kg's of his tissue to reach the MDL).
On the other hand, 210 Po is also found naturally in equilibrium as a result of the normal a-decay of 238U (or 210Bi (b)). No doubt there may be have
been good exposure to depleted uranium and or fuel/weapon manufacturing to KGB agents. So, there may be a small amount of Po in equilibrium with
anyone carrying around some quantity of 238 U inside of themselves .
As for radioisotope methodology goes, Po can be separated quite easily and multichannel alpha counting is quite specific. The sample is wet-ashed and
a shiny silver disk is added for sometime. The Po plates onto the disk, and can easily be concentrated and counted.
At the moment, I agree with the complicity of the diplomatic pouch...
Take care all,
O3
-Anyone who never made a mistake never tried anything new.
--Albert Einstein
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Pyrovus
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| Quote: |
Either the 210 Po is in fact rather clever *or* a red herring. 210Po would have the advantage of being very toxic while transmuting rather quickly
into 206 Pb |
A half life of 138 days is 'rather quickly'? Assuming they get around to doing an autopsy within about a year or two of a murder involving Po-210,
they'll still be able to detect the radiation produced by it.
Never accept that which can be changed.
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Jdurg
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| Quote: | Originally posted by Ozone
On the other hand, 210 Po is also found naturally in equilibrium as a result of the normal a-decay of 238U (or 210Bi (b)). No doubt there may be have
been good exposure to depleted uranium and or fuel/weapon manufacturing to KGB agents. So, there may be a small amount of Po in equilibrium with
anyone carrying around some quantity of 238 U inside of themselves .
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The half-life of U-238, as well as all of its daughter products, is so unbelievably long that if you had a kilogram of U-238 you'd only have a few
nanograms, if that, of Po-210 in there.
\"A real fart is beefy, has a density greater than or equal to the air surrounding it, consists of the unmistakable scent of broccoli, and usually
requires wiping afterwards.\"
http://maddox.xmission.com. |
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JohnWW
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In spite of its low level of radioactivity and its half-life of 4.5 x 10^9 years, U-238 itself is very toxic, although chemically as distinct from
radioactively. This toxicity would be far greater than the radioactive toxicity (due mainly to the damage done to quickly-dividing cells, such as
those in the gut and liver and bone-marrow, by high-energy alpha-particles, which can also cause cancer) of the equilibrium amount of Po-210 iin its
decay products. Have you heard about the cancer deaths (including of U.S. Army personnel) and birth deformities due to the use of depleted uranium
bullets and shells in Iraq by the Bu$h régime to obtain greater penetration of targets (on account of the hardness and high density of U)? Such
processed depleted uranium would have only very minute amounts of decay products in it.
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