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DBL%20Hendrix%20small.png College chemistry, 1983

Derek Lowe The 2002 Model

Dbl%20new%20portrait%20B%26W.png After 10 years of blogging. . .

Derek Lowe, an Arkansan by birth, got his BA from Hendrix College and his PhD in organic chemistry from Duke before spending time in Germany on a Humboldt Fellowship on his post-doc. He's worked for several major pharmaceutical companies since 1989 on drug discovery projects against schizophrenia, Alzheimer's, diabetes, osteoporosis and other diseases. To contact Derek email him directly: derekb.lowe@gmail.com Twitter: Dereklowe

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February 9, 2011

Thallium Poisoning? In This Day and Age?

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Posted by Derek

Thallium poisoning? Now someone in the lab has really lost it. But that seems to be what happened in New Jersey, with a chemist from Bristol-Myers Squibb accused of doing in her husband.

A note to the Newark Star-Ledger and some other newspapers: even though a hot isotope of it is occasionally used in medicine, the thallium in this case was not radioactive. It doesn't have to be; it's a good old-fashioned chemical poison. The element enters cells readily, being taken up as if it were potassium, but once it's there it starts disrupting all kinds of processes by latching on to sulfur atoms. It was good enough for Agatha Christie to use it for one of her plots, which (interestingly) seems to have publicized it enough that several other thallium plots were discovered or foiled because of her novel.

As even Wikipedia points out, thallium was "once an effective murder weapon", but the emphasis is one "once". That time is long past. Forensically, it's not the first thing that you think of, certainly, but it got picked up at autopsy in this New Jersey case. And it's not like there's any other way a person could get a high level of the element in their tissues, nor, with modern analytical techniques, can it be mistaken for anything else. Honestly, anyone who believes that they have a good chance of getting away with a thallium murder is just not thinking the whole business through.

There are no details about how the crime was done, but we can assume that some kind of soluble thallium salt was put into the victim's food. Thallium chloride is the cheapest source (as usual - Primo Levi was right when he said "chlorides are rabble"), but I'm not sure how cost-conscious the accused was. She very likely got the compound from work - and even there, it wouldn't surprise me if she had to order it up on some pretext, which will certainly make the investigation easier. Thallium's not a very common metal in organic chemistry - I've seen some uses for it, but nothing compelling enough to make me want to try it.

It's odorless and tasteless stuff, by all accounts. But it's a stupid poison. I'm not going to speculate on better methods - I haven't put that much thought into the topic, really - but there have to be some, possibly with obscure and nasty natural product toxins. Not that it's so easy to get ahold of those, but the Engineer's Triangle still applies, to murder as to everything else: Good, Fast, Cheap: Pick Any Two.

So in the end, we have what looks like a vindictive (but not very competent) poisoner, a dead victim, and all kinds of trouble and fallout for the innocent bystanders in all the families concerned. A sordid business.

Comments (63) + TrackBacks (0) | Category: The Dark Side | Toxicology


COMMENTS

1. Wagonwheel on February 9, 2011 1:32 PM writes...

Well this'll lighten the mood around these parts

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2. Jon on February 9, 2011 1:38 PM writes...

New Jersey, eh? The guy should have gone to Princeton Plainsboro, where House would have figured out it was thallium poisioning at about 8:57 PM, after nearly killing the patient about four times.

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3. wwjd on February 9, 2011 1:47 PM writes...

NPR had a report earlier this week about how few deaths actually get an autopsy. The one they featured was a woman in Oklahoma who had a gunshot to the chest. The boyfriend said it was suicide, so they didn't do an autopsy. I'm guessing the thallium lady never thought they would check for cause of death.

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4. Sili on February 9, 2011 1:49 PM writes...

Shoulda used heavy water instead.

Embarrassing how poor my memory is. I seem to recall there being a nice insoluble salt that's specific for Tl, but I'll be damned if I know which one. Still that might make for driving organic substitutions along the -Cl to -I in acetone lines.

Isn't it also used as a dopant in scintillators and the like?

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5. Hap on February 9, 2011 1:50 PM writes...

It's been done at least twice in recent memory in the US, once in FL by an ex-chemist who didn't like his neighbors (and left then a six-pack of soda with a little something extra in it - see the reference to George Trepal in the Wikipedia article here), and once by a woman in PA trying to remove he husband with his tea (she apparently finished her husband off with a nice dose in the hospital, I think - see here). The former got caught in part because he used a similar scenario for a murder mystery at his Mensa meetings.

These killings seem darkly amusing, like Fargo, until you realize that real people died for the short-sighted fantasies of amoral morons.

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6. TM on February 9, 2011 1:58 PM writes...

Why didn't the doctors use Prussian Blue as an antidote? In the article, it says that the guy died a day after they discovered he had been poisoned using Thallium.

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7. Matthew on February 9, 2011 2:09 PM writes...

I'd like to quibble - if you have to find out in the autopsy I'd say it was a VERY effective murder weapon.
Now not so much if you want to avoid getting caught, but dead is dead.

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8. Hap on February 9, 2011 2:27 PM writes...

If you want somebody dead, then, it worked. If you wanted monetary or some other gain, though, then getting caught is sort of suboptimal (you don't want the lawyers sucking up all your hard-stolen cash, and it isn't the same spending the cash in the prison dispensary).

I didn't think thallium had any sort of antidote - once you have the symptoms of poisoning, it's already too late (like alkylmercury poisoning) to do anything about it. The symptoms are probably well-enough-known, though (particularly the hair falling out) that if someone dies with those symptoms, somebody will order an autopsy.

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9. Always looking on the bright side on February 9, 2011 2:54 PM writes...

Hrm...should start checking to see if there are any new job postings from BMS...

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10. milkshake on February 9, 2011 3:07 PM writes...

Derek, Tl(I) chloride is not very suitable as a poison because it is nearly insoluble - Tl(+) is an effective alternative to Ag(+) for scavenging halogens.
A much better poison is Tl(I) sulfate, nitrate and carbonate. (I was also told that Tl(III) nitrate adducts with organic compounds are exceptionally nasty too, even more so than the Tl(I)

The general rule is that you should not poison your family members if you are a chemist - it really gives the game away. And in any case heavy metals are such a poor choice (they do not get metabolized away, and they are readily detectable down to ppb levels). There are so many suitable ornamental plants and I can think of one-step procedures starting from common material found in freshmen organic lab...

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11. milkshake on February 9, 2011 3:13 PM writes...

@4 Sili: heavy water does not work, unless you plan to drown a person in a bath tub filled with D2O. To see any effect on living organism one needs to replace >60% of total hydrogen with deuterium.

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12. David Formerly Known as a Chemist on February 9, 2011 3:17 PM writes...

The only time I used thallium was to specifically direct aromatic iodination ortho to a phenol, using TlOAc and I2. Good times, good times.

And #9...sick, sick, sick.

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13. Biomarker on February 9, 2011 3:45 PM writes...

There was a Chinese TV series a few years back in which an old rich guy was poissoned by this. A college student in China bought the stuff online for pennies and poissoned a few of his classmates in 2007. Just a note.

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14. bad wolf on February 9, 2011 3:48 PM writes...

The article specifically calls it "radioactive" thallium, so they were really going for broke.

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15. Pestor on February 9, 2011 3:49 PM writes...

How about nicotine as à prime candidate for the optimal poison? Readily metabolized and there are plausible explanations for high plasma levels.

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16. Mad Scientist on February 9, 2011 4:29 PM writes...

Are they sure it wasn't caused by tainted food imported from China?

The posts on this blog are disturbingly diabolical.........

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17. tox path on February 9, 2011 4:36 PM writes...

You don't necessarily have to buy or order thallium. Although outlawed, quite a few really old garages/barns/outbuildings belonging to the elderly have old mole bat stored away in them. It isn't terribly uncommon for dogs and cats to consume the stuff (or be poisoned by it). Amazing what old pesticides/herbicides/rodenticides long since banned that you can find in such structures that have never been tossed.

Hair loss is a chronic toxicity effect (if the victim even lives more than a day or two). More likely this guy presented with an acute gastroenteritis, similar to what many of our nasty oncology agents can produce at higher doses. Not a pleasant death, although I can't think of any "pleasant" ways to die.

Talk to the Russians about knocking people off. They seem to be most creative: dioxins, ricin in umbrella tips, etc.

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18. johnnyboy on February 9, 2011 4:59 PM writes...

Insulin can be a pretty good killer. In my days as a diagnostic veterinary pathologist, we sometimes suspected it in case of insured racehorses dying suddenly (in general, racehorse trainers are not particularly nice human beings - at least where I worked). And there's the whole Von Bulow thing of course...

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19. Hap on February 9, 2011 5:00 PM writes...

I saw a novel that called thallium "Moscow metal" and claimed it was used in bullets for people the Soviets really wanted to see gone.

The two cases I saw on TV (and in one case, read about), it took a fair amount of time for the victims to die (also with Prof. Wetterhahn's mercury exposure). I assume poisoners aren't looking to kill people immediately and have the finger of guilt pointing at them - otherwise, they'd be better with a gun - but looking for slower deaths that might be inconspicuous.

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20. PSBrookes on February 9, 2011 5:07 PM writes...

We actually use it in my lab (thallium chloride) as a surrogate for potassium, in assays of K+ channel activity (see Circ. Res. 106, 1190-1196; 2010) There are probes available that fluoresce upon thallium binding, so these can be loaded into cells and used to measure Tl+ uptake in a fluorimeter. Invitrogen even sells a kit (named "FluxOR") for it, which includes thallium chloride.

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21. silicon scientist on February 9, 2011 5:09 PM writes...

Any spectroscopist knows that thallium can be had in mid-IR optics--KRS-5 and -6 are a mix of bromide and chloride or iodide. Grind up a broken window with a mortar and pestle...and you have a poison that never appeared on anyone's reagant roster.

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22. metaphysician on February 9, 2011 5:23 PM writes...

My vague understanding is that Thallium tends to get picked by people who want their victim to suffer for fairly prolonged periods. Not that there aren't other poisons that will do that, but I certainly wouldn't want to try and commit murder with methyl mercury, for example ( or be in the same room with the stuff! ).

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23. AlchemistOrganique on February 9, 2011 6:00 PM writes...

Aside from serving as bases and halogen activators in Suzuki cross-couplings (TlOEt), thallium salts can be effective oxidants. In SPPS, I've had decent luck with on-resin disulfide formation between S-Acm cysteines using thallium(III)trifluoroacetate.

I would be surprised if this lady stole the reagent from BMS. Doesn't the company have a regularly updated inventory or regulated dispensation of super-hazardous chemicals?

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24. tedthechemist on February 9, 2011 6:01 PM writes...

Was widely used in the lab I did my Phd in - Thallium trifluoroacetate for electrophilic substitution of electron-rich aromatics. I always recall several jam jars of prussian blue scattered around the lab. I think this only really works if you quaff it down VERY soon after the thallium-once in the blood stream, prussian blue is not much use since it is not absorbed.

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25. El Selectride on February 9, 2011 6:10 PM writes...

5: Took forever to finally nail the wife, too. Curley was doing renovations in the science building of a local college, which was the suspected source of the Thallium. Only after they exhumed him and examined his hair, did they discover that the poisoning began before he began that job. IIRC, the source of Thallium used was from household rat poison.

http://www.trutv.com/library/crime/criminal_mind/forensics/cyril_wecht/7.html

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26. UK Yankee on February 9, 2011 7:57 PM writes...

"It was good enough for Agatha Christie to use it for one of her plots, which (interestingly) seems to have publicized it enough that several other thallium plots were discovered or foiled because of her novel."

As I learned from listening to BBC Radio 4 earlier this week, the possibility of thallium being the source of the "Bovington Bug" was not considered until after the killer raised his hand and suggested it in a emergency public meeting the local officals conducted at the time. It was not until a copy of "The Pale Horse" was found at his home that all the dots were fully connected...

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27. monoceros4 on February 9, 2011 10:47 PM writes...

"The guy should have gone to Princeton Plainsboro, where House would have figured out it was thallium poisioning at about 8:57 PM, after nearly killing the patient about four times."

Oh, Lord, "House". The show where any poisoning or any disease really is diagnosed on the strength of its least likely symptom, even if none of the more obvious ones have ever presented themselves.

I've _wanted_ to use thallium for something, once: a while back I was struggling with electroless gold deposition and apparently even a minute amount of a thallium salt exerts a remarkable effect on the quality of the coat. Still don't really want to get too near the stuff, though.

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28. wcw on February 9, 2011 11:12 PM writes...

Good, fast, and cheap: have an evening in Manhattan, then push him in front of a truck.

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29. wcw on February 9, 2011 11:18 PM writes...

Boy, you really have to read the links:
> $1 million settlement in the traffic death of her first husband

She was clearly just bored with how well the fast, cheap and easy play had gone.

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30. AceTen on February 9, 2011 11:50 PM writes...

So if there are two old bottles of Thallium nitrate in my lab, that we will never use, I should probably dispose of them before I upset any of my co-workers?

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31. Anonymous on February 10, 2011 2:52 AM writes...

Reminds me of that poisoning that happened in then Glaxo in RDU. Lady wanted her husband gone, bought the required chemical (I believe some mercury containing compound), and gave him a serving dissolved in a beer : the poisoning happened at a bowling alley, where both of them were "playing", along with the man whom the lady was having an affair with.
Lovely stuff.

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32. mmr on February 10, 2011 3:16 AM writes...

There was a great film along similar lines back in the 90s. Also based on a true story:
http://www.imdb.com/title/tt0115033/

Permalink to Comment

33. RB Woodweird on February 10, 2011 7:21 AM writes...

On the other hand, if you wanted to off someone whose spouse was a chemist, thallium would be a pretty good method.

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34. Cadbury Moose on February 10, 2011 7:45 AM writes...

In fiction, Ngaio Marsh had one novel with thallium (acetate?) as the poison.

In fact... http://en.wikipedia.org/wiki/Graham_Young

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35. TM on February 10, 2011 7:48 AM writes...

The doctors _did_ try to use Prussian Blue as an antidote, but they were too late. Jon (#2): Incidentally, the doctor that was treating him was nicknamed "House." Ironic, indeed.

http://www.nj.com/news/index.ssf/2011/02/doctors_scientists_led_heroic.html

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36. Gerald McBoing Boing on February 10, 2011 8:38 AM writes...

I read somewhere that when a woman wants to off her husband, poisoning is the usual method. Seems women like poisoning's indirectness. Men prefer more direct means, i.e. guns etc...

Permalink to Comment

37. emjeff on February 10, 2011 9:28 AM writes...

"Women make the best poisoners"; a former professor of mine (a female toxicologist) made that statement to the class on her very first lecture.

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38. anon on February 10, 2011 11:21 AM writes...

#31 - I think that she had been dosing the guy for an extended period of time, in and out of the hospital. Her lover ended up killing himself. She only ended up in jail recently after a judge ruled that what her lover told his lawyer (before he killed himself) could be used against her in court.

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39. wearinbeads on February 10, 2011 12:24 PM writes...

my segue on this is that "The Documents in the Case" by Dorothy Sayer is my all-time favorite whodunnit (enantiomers, not heavy metals, but whatever).

Permalink to Comment

40. milkshake on February 10, 2011 6:12 PM writes...

what kind of enantiomers? One possibility I can think of is spiking Robitussin cough syrup with levomethorphane...

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41. MedChem on February 10, 2011 6:17 PM writes...

I did a lot of Suzukis with Thallium salt in grad school, and was nervous and double or triple gloved, and held my breath everytime I used it. It was the only thing that worked for that darn tricky transformation I was doing. Got me out of grad school.

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42. NC chemist on February 10, 2011 10:12 PM writes...

#31 and 38:

I thought she used arsenic? At least that was the best guess at the time. I lived in NC at the time and getting ready to move out of state. I remember thinking "A chemist killing with arsenic? How cliche"

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43. NC chemist on February 10, 2011 10:14 PM writes...

#31 and 38:

I thought she used arsenic? At least that was the best guess at the time. I lived in NC at the time and getting ready to move out of state. I remember thinking "A chemist killing with arsenic? How cliche"

From WRAL's site:

"Ann Miller Kontz pleaded guilty Nov. 8, 2005, to second-degree murder and conspiracy to commit first-degree murder in the Dec. 2, 2000, arsenic poisoning death of her then-husband Eric Miller, a pediatric AIDS researcher at the University of North Carolina at Chapel Hill.

Raleigh police spent nearly four years pursuing Kontz, a former chemist and researcher at GlaxoSmithKline, before she was indicted on first-degree murder in September 2004."

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44. Anon on February 10, 2011 10:22 PM writes...

I read once that it was a fad in Victorian England to take small amounts of arsenic. It is noted in small amounts to give a sense of euphoria.

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45. Anonymous on February 11, 2011 1:56 AM writes...

#42, I stand corrected. I was not sure about the actual "active principle".

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46. Steve Stokowski on February 11, 2011 10:19 AM writes...

I often used Thallium Malonate Formate (Clerici's solution)as a heavy liquid for mineral separations. It's useful if you need to seperate out very heavy minerals from a rock for age dating or bulk chemical analyses. But, you can do the same kind of analyses on a rock without doing mineral separations with the Ultrachron at UMass.

Steve Stokowski

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47. Stewie Griffin on February 11, 2011 1:31 PM writes...

#44
John Emsley's "Elements of Murder" talks about Arsenic being used (topically if I remember correctly) by women b/c it gives the skin a warm blush look. Turned out that some folks that used arsenic as a poison were not found guilty since the defense argued that the arsenic present in the dead body was a result of using arsenic beauty products.

Permalink to Comment

48. AnotherAnon on February 12, 2011 4:52 PM writes...

Since she was in Jersey, couldn't she have just paid some equivalent of Tony Soprano to carry out a hit on her husband?

Anyway, going back to chemistry, are there any good reasons to continue using organomercurials, thalliums, cadmiums, stannanes, or plumbanes in CC-bond forming reactions?

Permalink to Comment

49. Anonymous on February 13, 2011 7:25 PM writes...

OK, thallium is nasty and detectable. How about TMS diazomethane? ARRGGHH. Remember Magic methyl(methylfluorosulfonate)...nasty..next day death from extensive lipid and DNA methylation. Fortunately, you can't buy it anymore....but it can be made in the lab. Interestingly, it's inventor received the Nobel prize in chemistry in 1994!!! Scarey crap!!

Permalink to Comment

50. Hap on February 13, 2011 10:54 PM writes...

I'm not sure about the cadmium, lead, and mercury compounds, but for natural product synthesis, Stille couplings are supposed to be significantly more effective and stereoselective than the less hazardous Suzuki couplings (for things like discodermolide). You might be able to use fluoroalkylated versions for ready retrieval and high molecular weight (lower volatility), but they are (or at least used to be) sort of pricey.

Thallium is used for some oxidative reactions (though I don't know that you'd want to use it as stoichiometric reagent on scale) and as an additive for some of the natural product Suzukis that people do try (Kishi first used it in a key Suzuki coupling for the synthesis of palytoxin).

The loss of thallium could probably be circumvented, but tin I think would be difficult.

Permalink to Comment

51. Sili on February 14, 2011 5:26 PM writes...

The former got caught in part because he used a similar scenario for a murder mystery at his Mensa meetings.
Damn. I though Columbo was supposed to be fiction. Permalink to Comment

52. Sili on February 14, 2011 5:55 PM writes...

what kind of enantiomers? One possibility I can think of is spiking Robitussin cough syrup with levomethorphane...
Muscarine. Carl Th. read the relevant scene to us in first year org. chem., although I'd forgotten about the specifics until I happened to read the book, myself, some years later.

Also: thanks for ruining my clean murders method.

Permalink to Comment

53. Anon on February 15, 2011 1:24 AM writes...

It seems to me that the charges against Ms. Li are entirely unproven. There is no evidence reported that she even had access to thallium - just that she worked as a chemist at BMS.

Permalink to Comment

54. Hap on February 15, 2011 10:36 AM writes...

No, but she did get caught lying to the cops - that was why they held her in the first place. Not a good idea in any case, but when your husband has died under unnatural circumstances (and your first husband also went away curiously), well, murder charges shouldn't be a surprise, or totally unwarranted. (The first rule of investigation when somebody dies is generally "Cherchez la femme/le hubby".)

The initial presumption with thallium is that nobody but a chemist is likely to have access, though (as in the second case in #5 and #17 above, it's not a requirement). In concert with the above, it pretty well explains why Ms. Li was arrested. The police have been wrong before, and may tend to look for neat ways to "solve" crimes when the actual perpetration was far less neat, but "When you hear hoofprints, think horses, not zebras" works for cops, too.

Permalink to Comment

55. Anon on February 15, 2011 11:52 PM writes...

I have not seen the story about her first husband - only the comment that he died in a traffic accident. Hardly mysterious. And the accusation of lying is just that - an accusation. My point is that just the circumstances are not enough. For example, husband might have taken thallium intentionally himself to implicate the wife. Not rational, and perhaps less likely than murder. But murder by the wife has not been proven by any means.

Permalink to Comment

56. Hap on February 16, 2011 10:15 AM writes...

That's what trials are for. (Even there, all you have to do is prove beyond a reasonable doubt, so there's still a chance they didn't do it, but were still convicted.)

The presumption is, though, that the police have some (significant) evidence that something untoward happened before they can arrest her. If you hold someone for lying, you have to have some good evidence that what the person said wasn't true - more likely, the police do it because they are suspicious and afraid that you're going to wander away before they can charge you with something bigger since (unless you're the feds) they're unlikely to get much out of the prosecution of lying to them. Of course, if you didn't lie, and they arrest you anyway, well, it might put a crimp in any subsequent case the police initiate, so the police would be circumspect about arresting someone unless they have good evidence that the person actually lied to them.

In either case, the arrest isn't just a shot in the dark (probably - see Duke rape case for a counterexample).

Permalink to Comment

57. Fortescue Bullrout on February 19, 2011 3:41 AM writes...

There was a rash of Thallium murders in my part of the world- the North Coast of New South Wales, Australia- just after WW2. Always wives putting it (as rat poison) into the sugar bowl and suddenly losing their own sweet tooth. Must have been in interesting little grapevine going on there. They got away with it too, until forensics improved, the rumors became too much to ignore, and the hubbies were exhumed.
We have a treasured family heiloom here- a very rough looking sugar bowl with "Thallium" gouged into the side.

Permalink to Comment

58. Watson on February 25, 2011 7:42 PM writes...

I'm surprised nobody mentioned "The Young Poisoner's Handbook" - a true story that is told in a way that borders on farce, and is at times disturbingly funny. http://www.imdb.com/title/tt0115033/plotsummary

It's a must see just for the gruesome illustration of "the scientific method", proper documentation (e.g., the "lab notebook"), and experimental sabotage.

Permalink to Comment

59. Watson on February 25, 2011 7:46 PM writes...

Oops, I should have read between the lines, someone already mentioned Graham Young.

Permalink to Comment

60. Jane on September 11, 2011 9:51 AM writes...

Hi,
I was working and living on an Indian Reservation in northern Minnesota in 2009 and had my home broken into and food and beverages laced with Thallium. I could taste and later smell this, as well as feel the effects. No one else could, however. It has taken me two years to unearth this, not by any help from anyone in the medical, health, legal, environmental or any related entity. I had to beg a doctor to test me for it. Why do people think you are nuts if you say someone tried/is trying to kill you?

Permalink to Comment

61. Mrs. Anonymous BMS Researcher on March 14, 2013 10:54 AM writes...

#37, that is historically true right back to Medea of Greek antiquity, for whose country (Colchis) colchicine is named!

Permalink to Comment

62. Pugwash on March 25, 2013 8:13 AM writes...

I had to laugh at Milkshake's suggestion. I mean - would anybody test if the cough-syrup had dextromethorphan or levomethorphan. O-demethylation yields Levorphanol. I seem to recall that the metabolism of both isomers is identical. I know DXM causes false-positives for the cheaper 10-panel drug tests but it would indeed be a tough one to extract enough material from the victim's body to perform a polarimetry... and would you go to such effort unless you really had reason to think that this was the cause of death.

Permalink to Comment

63. Anonymous on July 15, 2013 12:40 PM writes...

And, here, via The Safety Zone: http://www.nj.com/middlesex/index.ssf/2013/07/jury_resumes_deliberations_in_murder_trial_of_monroe_woman_charged_with_poisoning_her_husband.html

It also explains why she was arrested for obstruction of justice - she lied about obtaining thallium and was caught, and had tried to leave the US with her kids to return to China.

Permalink to Comment

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A New Way to Estimate a Compound's Chances?
Meinwald Honored
Molecular Biology Turns Into Chemistry
Speaking at Northeastern