Licorice smelling and tasting alcohol used as a foaming agent for processing coal and making it fit for transport, got into the water supply from a spill that went into the Elk River, running Northeast of Charleston, West Virginny. Coal Country for sure.
Much hand wringing–but no risk apparent.
Enviros tremble with anticipation. Coal Bad, Chemicals Bad, people scared.
Send money to the people who care bout u. Anything with a name like 4-Methylcyclohexane methanol has got to be bad, if not to you to your unborn chilluns.
Organic chemists create scary names because they are descriptive. Methyl is one carbon with the hydrogens attached, methanol is a methyl group with an oxygen/hydrogen radical attached. cyclo hexane just means a ring of 6 carbon hydrogen units.
Some alcohols like methanol can make you sick for sure–blind even. However the dose and the nature of the chemical makes the poison. The crisis had a lot to do with the smell and the anxiety people have about chemicals. Public officials went overboard, but they feel obligated–don’t want people with matching t shirts screaming at them.
The precautionary principle was installed even though the safety data sheet wasn’t scary at all, and the warnings were for much higher exposures than what was in the water. The big problem is it smells so people knew it was there.
Lawyers are circling but other than anxiety and the remediation costs and short term water shortage, what damages? Since the safety sheet says eye irritation and headaches for high dose exposures, hopefully people will not be scared silly, but some will have headaches and irritated eyes for sure.
As the public officials said, there is no known risk to health then they proceeded to take the precautionary principle out and dust it off–can’t use the water to wash clothes? Really, how about to water animals?
I bet the cattle and horses got the water if they needed it and how could washing clothes or things in the house be harmful except maybe the smell if you are anxious.-
http://www.foxnews.com/us/2014/01/13/hundreds-report-exposure-symptoms-in-w-va-after-crippling-chemical-spill/?icid=maing-grid7|myaol|dl19|sec3_lnk3%26pLid%3D429445
“Decision Makers” is a WV produced interview program. The treatment Dr. Letitia Tierney got from the host, Bray Cary, a “media mogul” in WV terms, shows some of the difficulty in getting good information to our public: At first most news people were helpful, but now that they’ve found a noisy big drum, they keep beating it.
http://www.wowktv.com/story/24608885/decision-makers-guests-include-del-don-perdue-gov-earl-ray-tomblin-dr-letitia-tierney-us-attorney-booth-goodwin-mayor-danny-jones-and-dr
She is in the 3rd segment.
WV used to call Charleston “The Chemical Capital of the World.” Dow, Monsanto, Union Carbide, Bayer, and others have and/or do make their home in this valley. A whole lot of us, fewer now than in the past, are chemical engineers, or other workers in the chemical industries. I think that if this spill had happened in another part of the country, citizens would have been far more freaked out than our “West Virginny” population has been.
carcenogicity->carcinogenicity, and where I said “MCHDM” above it should be CHDM, cyclohexane dimethanol
Why would anyone even be concerned about ppm methanol? The natural level for MeOH in human blood is around 1 ppm (1 mg/l) . Maybe we should look at it this way – since this whole class of alcohols seems to be so benign, has anyone ever found any saturated aliphatic alcohol that has any demonstrable teratogenicity, toxicity, or carcenogicity at aqueous ppm levels, and if so, what is it and why?
MeOH is ~1% of the crude MCHM. We don’t know what dilution/destruction factors going to through the drinking water plant, the percentage of the passing MCHM in the river going to the plant. You then have to come up with consumption rates. I’d bet the quantity consumed is pretty low.
Well, I’m not an expert in it by any means – my competence in o chem ends at knowing what to look up and how to look it up.
That WHO study, just by dumb luck I guess, happens to use cyclohexane carboxylic acid as one example of how oxygenated alicyclics are metabolized. There’s another study by Plapp et al. that addresses how mouse ADH-1 works with similar alcohols and even includes quantitative data on CHM. http://books.google.com/books?id=3FfUHK_tIxgC&lpg=PA125&ots=mjG3m7GQxj&dq=mouse%20alcohol%20dehydrogenase%20ADH-1%20methylcyclohexane%20methanol&pg=PA125#v=onepage&q=cyclohexyl%20methanol&f=false
Ben, you are a treasure for curious people.
Please consider putting up another commentary.
My problem is I know that methanol is a bad boy, but it’s bad because the body with alcohol dehydrogenase turns it into formaldehyde that turns into formic acid.
Just because a compound has a methanol stuck on the end of it, doesn’t mean it’s metabolized like methanol. Alcohol dehydrogenase may see a bulky molecule and just allow us to pee it out instead of turning it into a poisonous metabolite. In Fact it may be impossible for the MCHM to make formaldehyde then formic acid because the hexane and methyl group would have to be broken off to have a chance to make methanol into formaldehyde and then metabolize to formic acid.
Alcohol dehydrogenase is the key–it makes methanol into formaldehyde that goes to formic acid that damages or kills. The Rate limiting step is the alcohol dehydrogenase action on the methanol. We don’t even know if alcohol dehydrogenase would work on MCHM. Incidentally, we treat methanol tox with alcohol, keeps the alcohol dehydrogenase happy and busy, and the patient drunk, so the patient pees out the unchanged methanol.
Everyone assumes MCHM is going to make formaldehyde that would go to formic acid and burn people up big time–I see nothing in the lit that has been bantied about to indicate such a thing is the result, even if someone had a big time dose, which is not possible, given the dilutions that occurred.
Most of those compounds listed in the crude MCHM data sheet are just the various derivatives of MCHM and MCHDM, the carboxylic acids, the esters, the ethers. They’re very freely interconvertible in small quantities, especially in the direction of the carboxylic acids. By the time it comes out in your pee, it’s all going to be digested into various hippuric acids anyway, right? If you know even a tiny little bit of organic chemistry, you can easily find data on the unmethylated molecule, CHM, the dimethylated molecule, and the isopropylated molecule, p-menthan-7-ol, and they are literally natural and artificial flavors. One of them is GRAS listed by some organizations. There’s a WHO study that covers the safety of this whole class of compounds, since they’re quite widely found in foods, beverages, and lotions, in 1000s of variations. Due to the sheer variety, it’s conventional to look at chemicals like this more as a class of substances than one particular species, though obviously the more specific you can get, the better. I tried to post a lot of that info last week on your buddy’s blog at the Environmental Defense Fund site but I guess he blocked it because chemistry was upsetting the nutbars. I put it up with the references over on wikipedia where it can’t get censored though.
I usually defer to toxicologists, but this time I have a few quibbles. I agree with Tadchem more than I agree with you on toxicity. Basing the toxicity on methanol means that a huge dose of the crude product is required to reach the limit.
As for human ingestion. The spill was of estimated quantity over time into a flowing river. I haven’t seen an estimate of the concentration at the intake at American Water. The water plant has purification, including activated carbon and assumed it could handle the chemical. It overloaded the carbon. I can’t find any analyses of the component concentration in the water. Shutting down water consumption until you can’t smell the major component seems like a reasonable method for consumers, assuming American Water is actually doing water analysis.
Nasal chromatography is a pretty good way to detect very low concentrations.
Your comments trouble me.
Second hand reports on rashes. I am waiting for something other than what can be produced by the typical hysterical epidemic.
In fact, I am beginning to think you are an hysterical epidemic.
Could that be? Let’s consider the real world even with the deadly Crude MCHM that you say is awful stuff.
The Freedom tanks are at 2.3 miles from the junction of the Elk River with the Kanawha River in Charleston.
The Elk is 166 feet across at the Freedom tanks.
Water from the Elk is used in a number of counties.
The Elk is 250 feet across at the junction with the Kanawha
The Kanwha River is 700 feet across at the junction with the Elk in Charleston.
Consider, my friend, the dilution factor. The Elk river is no trickle. 15 miles up the Elk at Falling Rock the river is still 156 feet in width. It’s flow starts for the last stretch from Sutton lake at 50 plus miles from Charleston and it is a big river from Sutton lake, fed by a dam release. I know droughts, and I don’t hear of any droughts in West Virginny.
I am very suspicious of the “rashes” you say appeared, 100 of them reported at emergency departments. I am an emergency department physician and I know we have no patience with people who are working on their lawsuits, and usually the reports of a rash are from a less than serious effort to determine a toxic effect.
I would suspect there will be all kinds of people who go to the emergency department claiming headaches, since that is a listed side effect.
As for your claims with regards to crude MCHM I will defer to chemists and the MSDS on the contents of the crude stuff, but remind you “dose makes the poison” and admonish you in the most respectful of terms to consider what you’re claiming. How many acre feet of water are we talking about in the lower 2 miles of the Elk and it is a flowing river. I see no dam at the Charleston junction of the rivers.
Smells like licorice is not the best way to convince me someone is being poisoned. Anyone.
However there is always the green poultice that people look for in these terrible “spill” situations. I stand by my analysis, anxiety is not a toxic exposure. Toxicity is not a maybe, and dose, dose, dose, determines the toxicity.
John Dale Dunn MD JD Consultant Emergency Services/Peer Review Civilian Faculty, Emergency Medicine Residency Carl R. Darnall Army Med Center Fort Hood, Texas Medical Officer, Sheriff Bobby Grubbs Brown County, Texas 325 784 6697 (h) 642 5073 (c)
My point about methanol is that it is 100 times less toxic in rats than crude MCHM, so absent more info on crude MCHM, we’d be wise to set an oral reference dose–how much is safe to drink per day per kilogram of body weight–that is at least 100 times less than the ORD for methanol. you also err in thinking that the results of rat studies apply equally to humans. Rats aren’t human, and because of the uncertainty involved in applying the results of one species to another, toxicologists divide the result by uncertainty factors –usually 10x each– to err on the side of caution. In this case, CDC wisely applied three UFs, for a total reduction of 1000x, but they stupidly applied this to toxicity data for the wrong chemical — pure MCHM — rather than the crude MCHM that actually spilled data. For an explanation of exactly how they came up with the 1ppm level they consider safe, see
http://emergency.cdc.gov/chemical/MCHM/westvirginia2014/index.asp. Eastman Chemical –to its credit– has now posted all the tox studies it did on both crude and pure MCHM. see
http://www.eastman.com/Pages/Eastman-Crude-MCHM-Studies.aspx
Note that the crude mixture is significantly more toxic than the pure [it has lower LD50s in rats], and note also that both are more toxic to females than males.
The cruel joke is that after a week of hoo-ha about what level is safe, CDC said that people should keep flushing their taps until they can no longer smell the licorice odor.
But the ability of humans to smell low concentrations of anything is notoriously variable, varying by 100-1000x for almost every substance tested.
John — I actually agree with some of what you wrote. But you are misinformed about the spill in WV. All quoted published sources agree It was crude, not pure, MCHM that spilled. The pure product is very expensive and sold in gram quantities by TCI for the fragrance industry. As for the effects, over 400 people have gone to hospitals seeking help for objective symptoms, albeit mostly skin rashes from bathing and showering. As an ER doc, do you really think these reactions were just psychosomatic chemophobia?
The LD50 for methanol (Rat – Route: Oral) Dose is 5628 mg/kg [as reported by BDH MSDS Number: BDH-130]. For a 50 kg human exposed to 1% methanol, that’s about 28 kg of Crude MCHM.
The Eastman MSDS you cite for Crude MCHM reports TLVs, STELs, RELs, and TWAs that are all at least 200 ppm, as determined by ACGIH, NIOSH, and CCR Title 8, so your 1 ppm concentration and your “0.5mg/day for a big adult and 0.05 for a small child” dose are not based on actual toxicity values.
The ORD only refers to what the EPA has arbitrarily decided is the ‘maximum acceptable oral dose of a toxic substance’. The methods and procedures of the EPA for arriving at its results have been widely discussed on this forum, and are far more political than scientific.
I will credit you for your honesty in admitting to being a toxicologist. You have a vested interest in promulgating chemophobia.
Except for water and table salt, all foods contain carbon, with an average of about 1000 parts-per-trillion of *RADIOACTIVE* carbon-14.
no problem
If your are a professional toxicologist you must be familiar with the junk science used by the EPA to establish carcinogenicity and toxicity, and although the MSDS on Crude MCHM may include some scary stuff, that presumes of course it is the crude stuff, and that wasn’t what was reported, but it also assumes, what every toxicologist should have on the wall–the dose makes the poison.
As a practicing emergency physician who treats tox cases and teaches residents about tox, I am always reminded “the dose makes the poison.”
Of course you could make up a scary scenario like some have, but you know the presence of an odor is not and cannot be a measure of toxicity and the dilution factor for this spill is so immense that it was silly for them to do anything other than tell people to use bottled water and the smell would disappear with a short period. Instead they create this big deal because chemophobia seems to be the only part of science that journalists/politicians/chattering class people know.
Now we’ll have the West Virginny MCHM syndrome like the Gulf War Syndrome and the Agent Orange and Dioxin and radon panics. If you think I have chosen inappropriate comparisons, then you are on the bus with the chemophobes, but that would make you a professional toxicologist who is working the anxieties instead of doing good tox–I assume you to be a rational professional aware that mentioning the 1% methanol level in the crude was a distraction, considering the exposure from the spill in a big river.
Methanol is a bad boy, but dose, dose, dose is the critical factor, and the public got the scare stuff and the precautionary principle nonsense. I think it sad we have come to this as a society–scared out of our wits every time some blow dried TV journalist pronounces a crisis grabbing the kids and running for cover.
And you know those claims had more to do with psych and tox.
I recommend for all tox people and the last two Residency directors we had were Board Certified Medical Toxicologists, the book Hystories Elaine Showalter, that describes hysterical epidemics over the years. We should always be on the sketpical alert when we here the following words-syndrome, epidemic, crisis, threat, and see anxious frowns on the faces of main stream media anchors, followed by cherry picked interviews of “victims” and advocates.
Sorry I didn’t see the Millor typo. My bad. Please correct this first if you post my comment.
I do not expect that John, Junkman Milloy or anyone else on this list can understand this, but the chemical that spilled was not just “MCHM” — it was a mixture called “crude MCHM” — the MSDS is at
http://mediad.publicbroadcasting.net/p/wvpn/files/201401/MSDS-MCHM_I140109214955.pdf — and the only non-toxic ingredient is water at 4-10%. The other 90-96% of the product are toxic and would kill you if you drank it because it also contains 1% methanol.
The only LD50 dose info available on crude MCHM –the dose that kills 50% of the animals to which it is exposed– are for rats and minnows. So how can toxicologists estimate what level might be safe for humans to drink based only on what level kills animals?
We compare these levels with the extensive data available on other chemicals in the mixture, like the methanol. The methanol LD50 for rats is 100x higher for minnows 1000x and the daily Oral Reference Dose allowed in drinking water by EPA is just 0.5 mg/kg/day, or 50mg/day for a 100kg person but just 5mg/day for a 10kg child. This means CRUDE MCHM is 100 to 1000x more toxic in animals and so its ORD for humans should also be 100 to 1000x lower than for methanol– about 0.5mg/day for a big adult and 0.05 for a small child.
In contrast, the 1ppm concentration that EPA and CDC say is safe is not even a dose limit. This depends entirely on how much water you drink every day, how long you shower or bathe in it, etc. But 1ppm of anything by weight in a liter of water [which weighs 1 kg] is 1mg, so drinking one liter would give you about 1mg of crude MCHM — which is 200 times the ORD that I estimated above for children [remember them?].
But what do I know? I’m just a toxicologist.
extraordinary note. thanks.
one of the components of licorice? Gee, that could be one of thousands of components. And causing high blood pressure? Is this the dose in one licorice stick? Or in the extracted/synthesized chemical in the 3 or 4 gram amounts isolable from about 500 licorice sticks? And should we ban salt too? It can cause high blood pressure—or death—when you take to much. But, By Damn! it will cause death if you take too little.
Auream mediocritatem…..sic dixit Horace long long ago.
Hey Mary, it’s not toxic. Stop your nonsense. You don’t understand, all your concerns are driven by your fears. It’s not toxic, and you are a perfect example for why the insane precautionary principle continues to drive silly crisis noise and panicmongering. I do not expect that you will understand. You are a lost soul looking for security and assurance. Grow up.
While it may be true that “the dose makes the poison” in many cases, having 75,000 gallons of a chemical released right at the INTAKE for the water supply in the area means that many people were exposed to far higher levels than would be normal say for coal processing. At the very least we should be concerned about any chemical company that has substandard means of storing chemicals. Even their secondary barrier against leaks did not work because there were visable CRACKS in it. Even if you believe that this PARTICULAR chemical is safe, there are others that have been proven to not be safe. Should we wait until people die before we come up with better storage and inspection standards?
Except that is not the chemical that was accidentally released into the water, 4-Methylcyclohexane methanol
one of the components of licorice can cause high blood pressure in the susceptible. Can’t recall the mechanism.
Over-exposure (like large amounts in the lungs) to Di-Hydrogen Monoxide can kill you almost immediately !
Should it be banned?
Lots of food and drink that smells of licorice are known to contain (E)-1-Methoxy-4-(1-propenyl)benzene. To the lay person it’s anethole, the chemical name of Anise oil.
Exactly
and radioactive potassium
BTW: I’ve noticed that references to the solubility of the substance now state that it is highly soluble. Compare the dates of what you find in a web search. It seems to have gone from slightly-soluble to highly-soluble in the past week.
Wikipedia: “It has been patented for use in air fresheners.”
I guess licorice/mint isn’t flavor of the month in WV.
Just think of the “fun” you can have with a spritzer filled with Licorice scent and a whole bunch of gullible people willing to suffer the “vapors” at the slightest hint of exposure.
NNNNOOOOOO we all going to die…… or not! 😉
There have always been lunatics running around with signs, saying the end is near….some things never change.
Proprionic Acid and Iso-Amyl-alcohol come to mind. Swiss Cheese and Banana’s BTW banana’s also have measurable levels of Benzene.
I’d like to see all “organic” foods forced to carry a label with the full latin name for every ingredient.
“Oh my God! This spaghetti sauce has Solanum lycopersicum in it!
You mention the scary-sounding names and there’s a rash of commercials now about products that only contain ingredients you can pronounce.
Okay, how many different compounds are there in milk? And how many could most people recognize or pronounce?
Just as the world is a germ bomb, the world is a mad scientist’s chemistry experiment. Some of them are dangerous in high enough doses. Some of the things that are very dangerous in high doses are also absolutely required to survive. Oxygen — easily pronounced, that — is one of them.