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The Dangers of Dimethylmercury (2019) (chemistryworld.com)
100 points by caaqil on Jan 22, 2022 | hide | past | favorite | 77 comments



Worked with a professor who knew this person. He talked about this not infrequently. All the grad students knew of the story as well, and would talk about it. Her death really shook up the NMR community. It was the reason we never use DEM in our lab, and why many try to avoid it at all costs even now. If I remember properly, and this was over 10 years ago, the reason its commonly used is to calibrate the spectrometers, so in some areas it gets hard to avoid.

Also, the article mentions you need nitrile gloves to protect yourself from it. This is not sufficient and is dangerously misinformed. You need silver shield gloves to protect yourself from it.


> Also, the article mentions you need nitrile gloves to protect yourself from it.

I don't see that. With respect to an OSHA bulletin, the article says:

  The bulletin also urged that, aside from wearing a face shield, anyone working with dimethylmercury should wear Silver Shield laminate gloves beneath abrasion-resistant outer gloves.
The mention of nitrile gloves is in a more general context:

  Sugden points out that, when dealing with toxic substances, labs have shifted from latex gloves to nitrile gloves, [...]


Yeah I wouldn't even want nitrile gloves on with the stuff.

It is worth explaining just what is wrong with it. Mercury of course is a toxic compound, but kids used to crack mercury thermometers in their mouths and suffer no consequences. Pressure gauges came with exposed tubs of mercury and you would get some on your hands and it was fine, even kind of fun to play around with. Felters famously felt symptoms after careers of using it, usually blamed on long term inhalation, but it required a long time and lots of exposure to get to that point. Many people received dental amalgams with mercury bases and while there has always been a conspiracy theory about it, it has never been acutely toxic enough to be mainstream—the shift to other composites has instead been driven by comfort (metal fillings conduct heat and cold at an unnatural rate) and aesthetics (the new composites are white instead of silvery).

The basic reason is that the body does not eat metal and does not know what to do with it largely. Even with the metals that the body uses, like cobalt, it wraps every atom of cobalt in a big old ring of carbon and that's Vitamin B12.

Dimethyl mercury, is different from normal mercury, in a similar way. The methyl groups are organic groups that your body is much more willing to absorb and process. So the latex is not protecting you nearly as much because latex is this organic natural filter that lets things through... But also your skin is not protecting you because this stuff can seep into your skin via those methyl groups, your cells are just like “oh you look interesting I can take you into my chemistry.”

So yeah, milligrams are all it takes, tiny trace amounts: but the reason that you don't think of it being quite that dangerous is that your exposure to the liquid metal version is an exposure to a form that your body is uniquely unsuited to process or absorb. Water off a duck's back. Even though the water contains neurotoxin, it just rolls right off. Even, in our case, when ingested. But add these little methyl groups, methylmercury and dimethylmercury and really any organic mercury molecule, it gets real bad real fast because it's no longer rolling off our backs, it's soaking into our feathers.


Felters were mad from exposure to mercuric nitrate, not metallic mercury: https://en.wikipedia.org/wiki/Felt#Carroting

Metallic mercury can poison you if you inhale enough of it, yes, but that wasn't what the felters were suffering.


When I was a kid I would take the mercury from tilt-switches and pour it from hand to hand.

So heavy and shiny!


To the author of dead sibling comment: please, notify authorities for proper disposal and cleanup. Mercury contamination is extremely dangerous and can cause problems to your or other families for generations.

While small balls of Mercury might not seem dangerous, their continued presence means Mercury will slowly seep into environment over years and decades.


Quite: see for example https://www.newscientist.com/article/mg12817450-800-the-merc... for an example of the effects of mercury contamination in a building used for Physics research in Cambridge UK


Thank you very much for taking the time to write such a fascinating comment!


Thank you for your explanation.


So what is the mercury compound they put in multi-dose vaccines?

EDIT: Thiomersal, and it looks pretty organic. I've read that it leaves the bloodstream quickly, but not seen solid evidence that its leaving the body.


> Thiomersal

Also known as Merthiolate, a very popular topical antiseptic when I was younger (very popular as in: at least where I lived, the go-to antiseptic for a small cut or abrasion was either Merthiolate, or Mercurochrome which is another mercury compound, or a hydrogen peroxide solution; every kid from back then is familiar with at least one, if not all, of these antiseptics). It was so popular that, now that it's no longer available, the Merthiolate brand has been repurposed for a completely unrelated antiseptic (Chlorhexidine), to cash on all that popularity.


My go-to for topical use is Lugol's Idoine solution. Not only a disinfectant, but appears to aid healing (scars in particular) and some claim is anti-cancer.


They used to put thimerosal in a bunch more vaccines.

Until the clamour of anti-vaxxers who insisted that the rise in childhood autism cases was a direct cause of it (despite no evidence to back the claim) got so loud that they stopped using it in childhood vaccines in 2001. And childhood autism rates continued to rise unaffected by the change, proving (again) that this was due to some other factor (more sensitive diagnosis being the most popular theory) and also that the anti-vaxxers were full of shit and had no idea what they were talking about.


I know we're not supposed to discuss downvotes, but can't help but be curious why parent was downvoted? Factual errors? Cuss words? No references? Disagreement in opinion? It would be more interesting if they left a comment.


I'm speculating, but maybe it seemed like an unnecessary / unconstructive rant as against a group.


Thiomersal/Thimerosal leaves the bloodstream more quickly - but that is a relative term. Like you said, I've not seen not seen solid evidence that its leaving the body - but even then the best guesstimates are still half a year in the body instead of a full year or more like methylmercury.

It can also cross into the brain if my memory serves me correctly. Thimerosal may not be deadly, but is certainty to be avoided if possible.


from: https://www.cdc.gov/vaccinesafety/concerns/thimerosal/index.... "Thimerosal contains ethylmercury, which is cleared from the human body more quickly than methylmercury, and is therefore less likely to cause any harm."


It's a nice step in the right direction, for sure. But, having worked paying jobs in both Chemistry and Product Safety: Not counting latex, nitrile is the bare minimum, really, when it comes to chemical resistivity, and it cannot handle heat (> 40 °C). But hot surfaces are very common in labs. Hands off of latex gloves, though! Not only are they no good against most chemicals, they can fill up like a sponge and soak your hands with them.


The article mentions it:

"The bulletin also urged that, aside from wearing a face shield, anyone working with dimethylmercury should wear Silver Shield laminate gloves beneath abrasion-resistant outer gloves. [...] Sugden points out that, when dealing with toxic substances, labs have shifted from latex gloves to nitrile gloves, which are less porous"


If I were a chemist and I had to work with that satan's brew I wouldn't trust any gloves. I'd want a proper waldo setup.


I think every blackboard organic chemistry class should be required to be taught with multiple repeated asides about the dangers of organometallic reagents. And other dangerous materials too. It's not just pushing electrons around, it's fucking with your life potentially.

And they send you into lab with only folk-story level preparation if you're lucky enough to have gotten that info from others, and one day there is in front of you a bottle of organo-tin looking not too dissimilar from any other less harmful reagent. Only saved from danger by some slightly older grad student saying, "be careful around that stuff" (again, if you're lucky).

I myself only knew about, for example, the dangers of ether bottles left for a long time, because of my own interest in happening to read about it. Not a single person in my entire undergrad/grad career mentioned it. Hydrofluoric acid. Other nasty stuff, etc.

It's a major oversight for student education -- to be taught the dangers of the subject you're about to be exposed to in real life.


Yeah, most of the time I've read about such compounds it was via blogs, like this one on dimethylcadmium:

https://www.science.org/content/blog-post/things-i-won-t-wor...

"I'm saddened to report that the chemical literature contains descriptions of dimethylcadmium's smell."


@stevespang - All your comments seem to be [dead] and I don't see an obvious reason why you would be shadowbanned after looking at the last several. You might want to talk to HN.


> It's a major oversight for student education -- to be taught the dangers of the subject you're about to be exposed to in real life.

Organic chemistry used to teach people to pipette with their mouth because the alternative was too expensive.

Okay. These are the level of cowboys in the field. The Austin Fire Department had to threaten to let the UT Chem Building burn to get them to straighten up.

Even Derek Lowe (https://www.science.org/blogs/pipeline) talks about teaching a lab where the ether solvent was giving him migraines for an entire semester.

And, of course, we have Mex Gergel's Superfund-level toxic dumpsites described in "Excuse Me Sir, Would You Like to Buy a Kilo of Isopropyl Bromide?"

Organic chemistry seems to attract these kinds of people for some reason.


I worked for one of the companies mentioned by Gergel which ended up as a Superfund site after it had closed. We distributed some of his creations and he some of ours.

There is always some risk in handling chemicals, even more so making new ones from scratch.

This does not so much attract those driven by risky behavior, rather those who can tolerate the risk remaining after effective mitigation.

With toxic chemicals it's good to have a safety culture.

Historically, with more common toxins like benzene, it was often handled without gloves up to at least the mid 1970's when the effects of long-term exposure became more widely recgonized.

Regardless from the very beginning benzene had always been handled with no smoking, lighters, or open flames, and with a respirator when the operator deemed necessary.

Most days gloves were just plain never worn except for well-recognized major immediate hazards like pure sulfuric acid, and disposable gloves had never become a consideration since they were plain latex which is not very chemically resistant, too thin & skin-tight, basically as the name implies "surgical" gloves for physicians & nurses to maintain a more sterile enviroment and protect the patients from contaminants on the workers' hands, not as much to protect the workers themselves.

Industrial nitrile gloves were already up to today's standards but these were orders of magnitude more costly than medical disposables, much thicker, not tight at all, can last for years and be easily slipped on & off quickly for instance every time an entry needs to be made in a lab notebook without taking the chance of touching the notebook with any contaminated gloved hands ever.

Workers were expected to take very good care of their prized modern nitrile gloves so they would be ready every time when needed, unfortunately this was so seldom that often they couldn't find their personal gloves quick enough, and poured the sulfuric without using them anyway.

Or perhaps even more risky, using someone else's gloves, other than the specific pair they had been issued and expected to provide dedicated care & maintenance of along with their personal respirator. You didn't need these things most of the time, but when you did nothing else would do. And you never knew how contaminated someone else's PPE might have been.

By the 1980's litigation was alarmingly through the roof everywhere and toxic chemicals are a very difficult-to-defend target.

Mandates came down for workers to wear nitrile gloves for every single chemical with any kind of hazard at all. Materials like acetone, dilute acids, brine solutions etc. that had been handled safely without gloves for generations now triggered the requirement. Some operators who seldom wore gloves now needed to wear them most of the time from that point forward. If you wore them all the time it was felt you were protected all the time. Culture changed. It became a no-brainer.

Cue the arrival of disposable nitrile gloves, the full-strength originals were just too expensive for everyday use. The inflation from 1971 to 1976 had made sure of that.

Culture changed further. Eventually the appearence of a gloved hand holding a test tube is no longer a red flag that it likely contains one of the very few (in most labs) highly toxics that truly require the most extreme care.

Today I've got workers going through pallets of disposable gloves for every pair of traditional personal nitriles.

Other companies haven't issued personal gloves of any kind for decades, nitrile or not.

And I never dreamed the doorknobs and keyboards on the office machines would become so suspect for toxins compared to how it was before gloves became ubiquitous. Lab notebooks today might be safer to handle only with gloves and not enter non-chemical offices.

Remember PPE stands for "Personal Protective Equipment" and its not very personal if it's a throwaway and can be treated like an afterthought rather than a personal possession.

This methylmercury fatality could likely have been prevented if the disposable nitriles had never arose.

No doubt the victim would have been wearing the thick non-tight original gloves instead, which might have provided protection anyway even though the nitrile composition is just not completely impermeable to this particular toxin. Would have to safely discard the contaminated non-disposable gloves also since this is a lingering hazard rather than something like an aggressive acid which can be washed off the gloves afterward.


Agreed, though of course not every organometallic reagent is alike. It's quite alright to let students try to do a Grignard reaction (the generation of the Grignard reagent being famously finnicky in the hands of beginners and experienced chemists alike) once they have safety training behind them, it's quite another thing to let them work with even more flammable, explosive or toxic compounds. Some other more benign organometallic compounds are porphyrin and phtalocyanine dyes and various nicely colorful coordination complexes. One other sad incident with organometallic reagents was the death of Sheri Sangji[0], she was scaling up a reaction involving tert-butyl lithium, which resulted in a deadly fire. It was thought the accident was a result of a series of safety failures (bad safety education, bad ppe, weekend work) and the university and supervisor were (imo, correctly) held culpable for creating the conditions in which such a horrible accident was possible. This one is also quite scary because many organic chemists will routinely use n-Bu-Li and occassionaly tBu-Li, the deadly and more pyrophoric agent involved in this accident as well.

[0]https://en.wikipedia.org/wiki/Sheri_Sangji_case


I'm a chemist done research. Information is known, but procedures are more often than not, not respected.

In perovskite research there is a lot of toxic and dangerous materials, e.g., people would still ignore it.

It's hard to explain but my experience in labs is easily explainable with covid. All started cautious but in the end most aren't that thorough and safe.


Yes. I've often heard (although it appears to be an open question[1]) that chemists have a significantly shorter life span than the general population.

[1] https://pubs.acs.org/doi/10.1021/cen-v049n010.p005


Even as a lay person I know that most fluorine molecules are not to be messed with.


Uh, except the stuff you shove on your toothbrush?

The high-dimensional surface of "threat to life" vs. molecule structure is super, super, non-convex.

Like H2O -> yay, H2O2 -> die, H2 + O2 -> fire

Like methanol -> die, ethanol -> fun, propanol -> die, butanol -> die, heptanol -> die, octanol -> die


1-Propanol acts like ethanol, but stronger, so you'll be fine if you don't ingest too much. 2-Propanol on the other hand (isopropyl alcohol) gets metabolised into acetone, which isn't great. And the only difference between the two is the way the atoms are arranged!


Acetone is in the breath of people who are on a keto diet.


That's likely a far lower concentration.

The dose makes the poison.


How different is the LD-50 between EtOH and 1-propanol?


My high-school chemistry teacher had this joke: "If you drink Ethanol you dance around people, if you drink Methanol, people end up dancing around you". For context, certain communities in India have people dancing around the funeral procession.


The rhyme I was taught: Little Johnny was a chemist, little Johnny is no more. What he thought was H2O was H2SO4.


> Uh, except the stuff you shove on your toothbrush?

Fluoride is an exception, only in small quantities, and only topically (lots of salts are toxic, and so are concentrated solutions).

By and large fluorine chemistry is a giant pile of nope, so staying away from it is an excellent rule and quite far from a “super, super, non-convex”.


Many marketed small molecules have fluorine in them, organofluorine compounds are sometimes in fact preferred because they are metabolically more stable than the non fluorinated compound. example of some drugs that have more than 1 billion $ sales/year net that contain fluorine: bictegravir,enzalutamide,elexacaftor,paliperidone,sitagliptin,olaparib,teriflunomide.


Some amyl alcohol isomers have been investigated as ethanol replacements because of the similar effects, albeit at lower doses, and an absence of a hangover due to less toxic metabolites. They're also commonly found in fermented beverages. Dose makes the poison and all that.


And that’s why I said “most”.


ChubbyEmu’s video [1] on this was quite good. (As is the rest of his channel, if this kind of stuff interests you.)

[1] https://m.youtube.com/watch?v=NJ7M01jV058


Chemists get trained to work with dangerous substances, that's a core part of the job. But Dimethylmercury is something else, it's far more dangerous than anything else someone in that field would ever encounter.

NMR is usually a pretty boring field in terms of stuff killing you. The most you can usually expect is someone sealing an NMR tube with something still reactive inside, which might blow up the glass tube at a later point. That tends to annoy the people managing the NMR spectrometers, so there are usually rules and procedures that should eliminate that risk.

Of course you examine all kinds of substances by NMR, so my previous statement is kinda wrong. If you work with really toxic substances, you also want to analyze them and put them into an NMR spectrometer. A huge difference here is whether you're regularly working with really dangerous substances or not. Many substances in chemistry are dangerous, but they're the kind of dangerous that every chemist is supposed to be trained for. But there is an enormous differences between a regular dangerous chemical and something like Dimethylmercury where a few drops through a nitrile glove can kill you. That needs an entirely different level of precautions than the ones you usually have in the lab. And it's the kind of danger that simply isn't worth it for most cases. If you're used to work with truly dangerous substances you can probably handle somethign like this safely, but the real danger is when people used to working with medium dangerous substances handle a truly dangerous substance like this without being really aware of the extent of the danger.

That chemical is simply far too dangerous to be a calibration standard, and that's why it isn't anymore.


How much if this is the fact that the folks dealing with this are used to “medium dangerous” chemicals?

I know some lab workers who deal with nuclear materials. They have insane security and safety protocols. And they’re pretty non chalant about it.

I also know some industrial workers who deal with conventional metals at very high temperatures.

Is this weird mercury really more dangerous than molten steel?

I suppose you could survive “a few drops” of molten steel on your hand, but you wouldn’t have a hand anymore.


Molten steel is not that bad, I think boiling water is worse.

I had a drop of molten steel fall on my bare skin, doing welding, the worst I experienced was a bit of pain and a small 1st degree burn that didn't require treatment and didn't leave a scar. I heard that with the proper technique it is possible to put scoop molten steel with your bare hands without burning yourself (not that I recommend it, obviously).

Metal tends to bead up (high surface tension), and the Leidenfrost effect offers temporary protection. I may be wrong but I suspect you are more at risk of burning yourself in a kitchen than in a steel mill. I would be more scared of a deep fryer than a crucible.


An equivalent size droplet of molten steel wouldn't take your hand off, unless the burn gets infected later.

Also, molten steel radiates IR and glows obviously, so you can usually tell when it's about, and doesn't stay molten and remain a silent, persistent danger.


This reminds me of the tragic case (involving a different compound) of Sheri Sangji[1], a research assistant at UCLA who spilled a pyrophoric substance on her highly flammable synthetic sweater that she was wearing instead of a lab coat.

[1] - https://en.wikipedia.org/wiki/Sheri_Sangji_case


I still remember this event when it happened. I was getting my PhD at the time. I think about it regularly.


I started my chem grad school about a decade later and all the changes were well accepted and the field was still mourning her loss. What a tragedy.


I wonder if the outcome would have been differnt if she had just immediately changed her gloves (or maybe she did? The story doesn't really say, but implies that she just continued the experiment).


After all, she had adhered to the safety regulations involving dimethylmercury.

Within weeks of Wetterhahn’s death, Chemical & Engineering News ran a letter on her lethal accident and the alarming results of a dimethylmercury test on the type of gloves she had worn.

It's interesting that no one ever tested them before that.


Note the time between initial exposure and death -- almost a year. Terrifying.


And about 5 month before any symptoms showed up, then comatose within 3 weeks.

I once asked a biochemist how that's even possible. Apparently it irretrievably destroys a part of the body's metabolism that is necessary to repair nerve cells.


When I was studying chemistry, latex gloves were not allowed in org chemistry lab as too many thing can go through them and they provide a false sense of security.


I didn't take chemistry past freshman general chem, but we didn't use gloves at all. Eye protection, yes.


Whilst it becomes political now, lab accidents and lab protection even for known risk is still happened. If you study something intensively and it will leak out with more probabilities.


This stuff is scary when you think it could be used in Putin-style assassinations.


It is now assumed that this already happened, in 2011, in a Bulgarian umbrella attack in Germany's crime capital, Hanover. My somewhat unfounded guess is that the perpetrator himself perished not too long after the victim, which would explain why the case is still unsolved.


It seems like it's easily detected though? Is there any legitimate reason in today's world for someone to have ~80x above mercury's human toxicity limit, besides those actually working with the stuff in the industry?


The assassins are too scared to handle it too

Coupled with the year long gap before death

Its probably not an ideal choice


Except for the most pressing assassinations, I imagine lag is a feature, not a bug.


[flagged]


It is not. The mercury in (some, but not all or even most, these days) vaccines is ethyl mercury. Here is an article that explains a bit more of the similarity with dimethyl mercury, though - they are both organic mercurials:

>Both ethyl mercury and Hg2+ are very neuro toxic compounds. However, ethyl mercury is more rapidly partitioned into the hydrophobic (fatty) tissues of the central nervous system and is a more potent neuro toxin than Hg2+ based on this “partitioning factor”. It is this partitioning factor that makes organic mercurials such as dimethyl mercury so neuro toxically lethal (this is the compound that caused the death of a Dartmouth University chemistry professor after she was exposed to a drop or two on her gloved hand).

>The concern with organic mercurials, such as thimerosal, is that such compounds can be perceived as “pro toxicants” just as certain pharmaceuticals can be classified as “pro drugs”. This means that the original compound, e.g. thimerosal, is less reactive giving the compound time to partition into certain areas of the body before it breaks down releasing the ethyl mercury and then further releasing Hg2+. However, while attaching ethyl mercury to thiolsalicylate makes the ethyl mercury less reactive it most likely allows increased partitioning into the central nervous system before the ethyl mercury is released and thereby, increases the neuro toxicity per unit ethyl mercury involved

https://vaccinechoicecanada.com/vaccine-ingredients/thimeros...


No its not as you pointed out but didn’t clarify. Ethylmercury is not the same as methylmercury.


I would think it would go without saying vaccines don't use one of the most toxic substances known by virtue of the fact people aren't dropping dead.


It took a year to die from 4mg of dimethyl mercury. If it took that long to die from injection with an excess of ethyl mercury, would we even find out why they died?


With a sample size that big and 100% fatality, i would say, yes obviously.


And, with selective, not 100% fatality, it being ethyl, not methyl mercury?


My comment was about how it was obviously not dimethyl mercury.

Whether or not we would detect some hypothetical unspecified toxic effect caused by some other substance would presumably depend on the nature of the effect and how prevalent it is.


Ethylmercury is used insted of (di-)methylmercury, because it is cleared from the body faster: https://www.cdc.gov/vaccinesafety/concerns/thimerosal/index....


But not nearly so fast as we are invited to believe.


> OSHA fined Dartmouth $9,000 (£6890) for what it considered the institution’s failure to provide adequate caution, particularly about the shortcomings of disposable latex gloves.

I would think that PhD. chemists would be responsible for buying their own PPE. Also $9,000 is such a weirdly small number


> I would think that PhD. chemists would be responsible for buying their own PPE.

I wouldn't; why would you?


Guessing / hoping they meant the chemists would be responsible for determining / ordering PPE suiting what they’re working on, not that they’re supposed to pay for it out of pocket.

Though from what I’ve heard about solid through sand buckets, and pitted face-shields, and contents of lab fridges, I’d think GP a bit optimistic.


> Guessing / hoping they meant the chemists would be responsible for determining / ordering PPE suiting what they’re working on, not that they’re supposed to pay for it out of pocket.

That makes more sense, thanks.


I'd expect standard PPE to be purchased by the chemistry department for all labs (charged back to individual research grants or just part of the "overhead" percentage they take out of all grant funding).

Anything specialty is probably specified by the researcher, and ordered and paid for by the staff person handling grant administration.


Who else is supposed to know how chemicals are supposed to be handled?


Their PI who is legally and morally responsible for everything that happens in their lab.


And everyone’s guidance was wrong at the time, so it doesnt make sense.

OSHA used the opportunity to make a statement that wouldnt be fought, compared to if they tried this with a much higher fine.




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