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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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January 30, 2014

The West Virginia Formaldehyde Claim Is Nonsense

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Posted by Derek

This morning I heard reports of formaldehyde being found in Charleston, West Virginia water samples as a result of the recent chemical spill there. My first thought, as a chemist, was "You know, that doesn't make any sense". A closer look confirmed that view, and led me to even more dubious things about this news story. Read on - there's some chemistry for a few paragraphs, and then near the end we get to the eyebrow-raising stuff.
4-MCHM.png
The compound that spilled was (4-methylcyclohexane)methanol, abbreviated as 4-MCHM. That's its structure over there.

For the nonchemists in the audience, here's a chance to show how chemical nomenclature works. Those lines represent bonds between atoms, and if the atom isn't labeled with its own letter, it's a carbon (this compound has one one labeled atom, that O for oxygen). These sorts of carbons take four bonds each, and that means that there are a number of hydrogens bonded to them that aren't shown. You'd add one, two, or three hydrogens as needed to each to take each one up to four bonds.

The six-membered ring in the middle is "cyclohexane" in organic chemistry lingo. You'll note two things coming off it, at opposite ends of the ring. The small branch is a methyl group (one carbon), and the other one is a methyl group subsituted with an alcohol (OH). The one-carbon alcohol compound (CH3OH) is methanol, and the rules of chemical naming say that the "methanol-like" part of this structure takes priority, so it's named as a methanol molecule with a ring stuck to its carbon. And that ring has another methyl group, which means that its position needs to be specified. The ring carbon that has the "methanol" gets numbered as #1 (priority again), so the one with the methyl group, counting over, is #4. So this compound's full name is (4-methylcyclohexane)methanol.

I went into that naming detail because it turns out to be important. This spill, needless to say, was a terrible thing that never should have happened. Dumping a huge load of industrial solvent into a river is a crime in both the legal and moral senses of the word. Early indications are that negligence had a role in the accident, which I can easily believe, and if so, I hope that those responsible are prosecuted, both for justice to be served and as a warning to others. Handling industrial chemicals involves a great deal of responsibility, and as a working chemist it pisses me off to see people doing it so poorly. But this accident, like any news story involving any sort of chemistry, also manages to show how little anyone outside the field understands anything about chemicals at all.

I say that because among the many lawsuits being filed, there are some that show (thanks, Chemjobber!) that the lawyers appear to believe that the chemical spill was a mixture of 4-methylcyclohexane and methanol. Not so. This is a misreading of the name, a mistake that a non-chemist might make because the rest of the English language doesn't usually build up nouns the way organic chemistry does. Chemical nomenclature is way too logical and cut-and-dried to be anything like a natural language; you really can draw a complex compound's structure just by reading its name closely enough. This error is a little like deciding that a hairdryer must be a device made partly out of hair.

I'm not exaggerating. The court filing, by the law firm of Thompson and Barney, says explicitly:

30. The combination chemical 4-MCHM is artificially created by combining methylclyclohexane (sic) with methanol.

31. Two component parts of 4-MCHM are methylcyclohexane and methanol which are both known dangerous and toxic chemicals that can cause latent dread disease such as cancer.

Sure thing, guys, just like the two component parts of dogwood trees are dogs and wood. Chemically, this makes no sense whatsoever. Now, it's reasonable to ask if 4-MCHM can chemically degrade to methanol and 4-methylcyclohexane. Without going into too much detail, the answer is "No". You don't get to break carbon-carbon bonds that way, not without a lot of energy. If you ran the chemical (at high temperature) through some sort of catalytic cracking reactor at an oil refinery, you might be able to get something like that to happen (although I'd expect other things as well, probably all at the same time), but otherwise, no. For the same sorts of reasons, you're not going to be able to get formaldehyde out of this compound, either, not without similar conditions. Air and sunlight and water aren't going to do it, and if bacteria and fungi metabolize it, I'd expect things like (4-methylcyclohexane)carboxaldehyde and (4-methylcyclohexane)carboxylic acid, among others. I would not expect them to break off that single-carbon alcohol as formaldehyde.
MeOH%20rxn.png
So where does all this talk of formaldehyde come from? Well, one way that formaldehyde shows up is from oxidation of methanol, as shown in that reaction (this time I've drawn in all the hydrogens). This is, in fact, one of the reasons that methanol is toxic. In the body, it gets oxidized to formaldehyde, and that gets oxidized right away to formic acid, which shuts down an important enzyme. Exposure to formaldehyde itself is a different problem. It's so reactive that most cancers associated with exposure to it are in the upper respiratory tract; it doesn't get any further.

As that methanol oxidation reaction pathway shows, the body actually has ways of dealing with formaldehyde exposure, up to a point. In fact, it's found at low levels (around 20 to 30 nanograms/milliliter) in things like tomatoes and oranges, so we can assume that these exposure levels are easily handled. I am not aware of any environmental regulations on human exposure to orange juice or freshly cut tomatoes. So how much formaldehyde did Dr. Scott Simonton find in his Charleston water sample? Just over 30 nanograms per milliliter. Slightly above the tomato-juice level (27 ng/mL). For reference, the lowest amount that can be detected is about 6 ng/mL. Update: and the amount of formaldehyde in normal human blood is about 1 microgram/mL, which is over thirty times the levels that Simonton says he found in his water samples. This is produced by normal human metabolism (enzymatic removal of methyl groups and other reactions). Everyone has it. And another update: the amount of formaldehyde in normal human saliva can easily be one thousand times that in Simonton's water samples, especially in people who smoke or have cavities. If you went thousands of miles away from this chemical spill, found an untouched wilderness and had one of its natives spit in a collection vial, you'd find a higher concentration of formaldehyde.

But Simonton is a West Virginia water quality official, is he not? Well, not in this capacity. As this story shows, he is being paid in this matter by the law firm of Thompson and Barney to do water analysis. Yes, that's the same law firm that thinks that 4-MCHM is a mixture with methanol in it. And the water sample that he obtained was from the Vandalia Grille in Charleston, the owners of which are defendants in that Thompson and Barney lawsuit that Chemjobber found.

So let me state my opinion: this is a load of crap. The amounts of formaldehyde that Dr. Simonton states he found are within the range of ozonated drinking water as it is, and just above those of fresh tomato juice. These are levels that have never been shown to be harmful in humans. His statements about cancer and other harm coming to West Virginia residents seem to me to be irresponsible fear-mongering. The sort of irresponsible fear-mongering that someone might do if they're being paid by lawyers who don't understand any chemistry and are interested in whipping up as much panic as they can. Just my freely offered opinions. Do your own research and see what you think.

Update: I see that actual West Virginia public health officials agree.

Another update: I've had people point out that the mixture that spilled may have contained up to 1% methanol. But see this comment for why this probably doesn't have any bearing on the formaldehyde issue. Update, Jan 31: Here's the MSDS for the "crude MHCM" that was spilled. The other main constituent (4-methoxymethylcyclohexane)methanol is also unlikely to produce formaldehyde, for the same reasons given above. The fact remains that the levels reported (and sensationalized) by Dr. Simonton are negligible by any standard.

Comments (112) + TrackBacks (0) | Category: Chemical News | Current Events | Press Coverage | Toxicology


COMMENTS

1. annonie on January 30, 2014 10:15 AM writes...

Said from the viewpoint of a chemist.

Actually, formation of methanol or formaldehyde or formic acid plus methyl benzene is not all that unreasonable, which could be done by micro-organisms.

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2. Puff the Mutant Dragon on January 30, 2014 10:20 AM writes...

I blogged about the West Virginia spill too, lol. The accident has wrought havoc with the water supply and caused a lot of people a lot of grief, but...there's no sense in spreading panic by making it sound like it's worse than it really is. It's kind of appalling that a scientist (Scott Simonton) would help promote this kind of nonsense.

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3. Wheels17 on January 30, 2014 10:21 AM writes...

My favorite example for non-chemists is the chemical that you have in your kitchen composed of a metal that burns and explodes when dropped in water, and a poison gas used in WW I.

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4. Chemjobber on January 30, 2014 10:24 AM writes...

Thanks for the links, Derek! I note that it was not me that found the lawsuit, but a reader of mine (and a chemist) who is sipping sub-ppb levels of MCHM in their water.

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5. SP on January 30, 2014 10:28 AM writes...

I wouldn't be surprised if there were other chemicals beside MCHM in the leaking tank that were not properly disclosed/reported- the company responsible seems to have been a shell expressly created for the purpose of shielding other real companies from liability, so they're not really motivated to spend much time being careful. But the reported level of formaldehyde doesn't support the argument that any formaldehyde precursors were there.

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6. Curious Wavefunction on January 30, 2014 10:31 AM writes...

Nice takedown. Not to mention that formaldehyde is naturally produced in the human body as the breakdown product of many enzyme demethylations. And it's even released by some antibiotic drugs like ampicillin prodrugs. The dose does make the poison. But none of thus will convince alarmist chemophobes.

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7. See Arr Oh on January 30, 2014 10:35 AM writes...

I've been trying all morning to retrosynthetically (take the molecule apart, backwards) disconnect MCHM to produce formaldehyde and "cyclohexyl anion," or some equivalent. I just don't see a feasible way, short of invoking some high-energy radical.

Anyone else?

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8. BG on January 30, 2014 10:36 AM writes...

What were these guys using 4-MCHM for? Only TCI sells it, and it's fairly expensive (5g = $105)

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9. db on January 30, 2014 10:48 AM writes...

8: don't know what specifically they used it for, but the company, Freedom Industries, sells (makes?) polymers and polymer blends for, somewhat ironically, industrial wastewater treatment.

A former employer of mine bought their polymers for sludge thickening operations and scrubber liquor clarification.

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10. Pig Farmer on January 30, 2014 10:55 AM writes...

Absolutely spot on, Derek. I'm the chemist who sent the lawsuit to Chemjobber a couple of weeks ago. I'm not drinking the water yet, not because I'm afraid of any possible toxicity, but I just don't like the taste of MCHM, and it has a very low odor threshold (0.5 ppb). You're absolutely right that this is written purely for the lawyers benefit, and is sloppy journalism and irresponsible scaremongering of the sort you always see when chemicals make the headlines. I also agree that the head honchos at Freedom Industries need to do some serious jail time over this, since it seems obvious to me that this is a case of criminal negligence. Fortunately Freedom Industries has been ordered to dismantle their facility on the Elk River, commencing no later than 3/15/14. Good riddance to them. I do, however, feel sorry for the workers who will lose their jobs over this. Meanwhile the President of this lousy outfit continues to live it up at his Marco Island mansion.

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11. Pig Farmer on January 30, 2014 11:00 AM writes...

http://en.wikipedia.org/wiki/2014_Elk_River_chemical_spill
MCHM is a foaming agent used to clean up coal.

Permalink to Comment

12. Anonymous on January 30, 2014 11:03 AM writes...

They use it to "clean" coal, I think specifically to separate out really small particles.

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13. Philip on January 30, 2014 11:09 AM writes...

"And the water sample that he obtained was from the Vandalia Grille in Charleston, the owners of which are defendants in that Thompson and Barney lawsuit that Chemjobber found."

I think you mean plaintiffs, not defendants. If I am wrong, please delete this post. If I am correct, please edit the story and delete this post.

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14. Bob Sacamano on January 30, 2014 11:11 AM writes...

David Zucchino wrote an interesting piece about this in the LA Times today (link in handle). It includes this gem about the other chemical (a polyglycol ether) involved in the spill:

"Then the chemical company responsible for the spill belatedly admitted a second, equally unpronounceable chemical containing ether also had been dumped into the water."

And now we have diethyl ether coming out of the taps. Remarkable.

The LAT is scrambling to correct the formaldehyde nonsense, but the ether reference remains.

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15. BG on January 30, 2014 11:12 AM writes...

Thanks 9 and 11.

7: You could do an elimination to make the the exocyclic alkene, ozonolyze and DMS quench to make formaldehyde and the cyclohexanone. Then do a Wolff-Kishner reduction on the ketone to the alkane.

You could go directly to the methylcyclohexane by oxidizing the alcohol to the aldehyde then doing a rhodium catalyzed decarbonylation- but I don't know of any ways to reduce the CO to formaldehyde.

Or as you pointed out you could invoke high energy radical intermediates: Blast the stuff with gamma radiation and pray that the correct bonds break and the correct bonds form in the resultant chaos.

Obviously none of these processes are happening in the river.

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16. cirby on January 30, 2014 11:13 AM writes...

Considering that the lethal dose of MCHM in rats is pretty high (825 mg/kg), and you can taste the stuff at fractional parts per billion...

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17. Hap on January 30, 2014 11:14 AM writes...

I can see P450 oxidizing next to the alcohol on the cyclohexane, but even then it probably wouldn't fragment to formaldehyde and 4-methylcyclohexanone. If you oxidized 1-HO-4-CHM to the aldehyde, retro-Claisen might get you formate and 4-methylcyclohexanone. Fragmentation conditions to give you formaldehyde would probably give you formate and/or methanol by Cannizzaro reaction or formic acid/CO2 by oxidation.

When someone can make lots of money (or thinks they can) by not knowing something, this is what happens.

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18. NoDrugsNoJobs on January 30, 2014 11:18 AM writes...

Perhpas more relevant to what levels of formaldehyde are problematic, normal human plasma levels of formaldehyde are around 2.6 uG/mL; actually fairly high when you consider that the half life in plasma is about 1-2 minutes! This is a pretty high background (baseline) level, particularly on a molar basis. Drugs that have the ability to oxidize a methyl (phenol methyl ethers) or hydrolyze a methanol (methyl esters)will also generate formaldehyde and formic acid (formate). This is generally not an issue in view of the high daily endogeneous production and metabolism of formaldehyde. Its most troubling effects tend to be site specific (inhalation, skin contact) where a localized concentration might be higher and pass the tolerability thresholds.

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19. Curt F. on January 30, 2014 11:19 AM writes...

Can someone explain (using either IUPAC nomenclature or even historical arguments) why methylcyclohexanemethanol ever came to be a commonly used name for the chemical? Wouldn't either 1-hydroxymethyl,4-methylcyclohexane or (4-methylcyclohexyl)methanol be much better names than methylcyclohexanemethanol?

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20. See Arr Oh on January 30, 2014 11:22 AM writes...

@BG, @Hap - Yeah, those all seem viable to me. As Hap points out, most oxidative fragmentation or rearrangment conditions give formate, which (thankfully) won't raise an environmental ruckus.

But BG has the truth of it: None of these potential reactions happens in water at 20 deg C, even when invoking microorganisms.

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21. JS on January 30, 2014 11:22 AM writes...

For what it's worth, the spill is generally said to be of "crude 4-MCHM". And according to the Eastman Chemicals SDS, that is a mixture of a number of related compounds, plus 4-10% water and 1% methanol. (SDS is linked in name.)

I totally agree with Derek's post; I'm just trying to put a little more information out there.

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22. qvxb on January 30, 2014 11:23 AM writes...

1 ng/mL = 1 µg/L = 1 ppb = 0.001 mg/L = 0.001 ppm

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23. Gene on January 30, 2014 11:25 AM writes...

Understanding chemistry? I had zero chemistry in grade/high school. That paragraph on nomenclature is more formal training than I've ever had.

I only understand most of this stuff because I'm a computer science guy, and it's got the same sort of formal logic to a lot of it, plus there's Google now.

However I don't understand the lawyers, as their chemistry errors could be a way for the opposition to win, since their lawsuit is wrong on facts. They need to be up on this.

These guys look like the sort that would fall for the dihydrogen monoxide bit in a heartbeat.

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24. oldnuke on January 30, 2014 11:37 AM writes...

No doubt the formaldehyde in the water supply is from a V-8 juice spill a few years ago.

I wonder how many WVa teachers are capable of explaining why this is junk "science"?

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25. PPedroso on January 30, 2014 11:38 AM writes...

Love these type of posts! Thanks Derek!

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26. Chemjobber on January 30, 2014 11:39 AM writes...

Worth noting (link in my handle) that there is 1% of methanol in crude MCHM, according to Eastman. So it's not especially surprising that formaldehyde might be detected in the water? (dunno how fast air oxidation of MeOH to formaldehyde happens... not very, I'd assume.)

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27. Anon8 on January 30, 2014 12:06 PM writes...

Derek: You go at length to describe the chemistry, nomenclature and other sane logic that we the chemists fully agree but at the end of the day the jury that gets hired to settle on these and other issues will not be the chemists! They will be not included in the jury pool by systematic elimination by the lawyers in a pre-trial move. Not long back we had one of those safety meeting for the chemists, the OSHA regulation etc. Guess what, the guy who preached (the do’s and do not) was not even a chemist, but was a lawyer. I reached the conclusion that we the chemists will never win. When you are going to litigate an issue that is full of emotions, the rationality takes the backseat

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28. Hap on January 30, 2014 12:07 PM writes...

21: It's probably (although I don't know how they made it) a Diels-Alder/reduction product from isoprene and acrolein, so probably parent aldehyde might (probably not) be around and D-A regioisomers in addition to diastereomers of 4-MCHM. (I'm assuming the reactants were distilled off, probably before reduction.) There could be aromatized product (3/4-methylbenzaldehyde) present as well. (The benzaldehydes would probably go to benzoic acids under ambient conditions, which aren't going anywhere I think.)

None of these, though, have a really good path to generating formaldehyde under ambient conditions. The 1% MeOH could easily generate formaldehyde through biological oxidation but probably can't generate it at a very high concentration (air oxidation, as Chemjobber noted, probably is glacial).

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29. Pig Farmer on January 30, 2014 12:17 PM writes...

http://en.wikipedia.org/wiki/4-Methylcyclohexanemethanol
MCHM is a by-product from hydrogenation of dimethyl terephthalate

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30. Hasufin on January 30, 2014 12:21 PM writes...

Thank you so much for the clear explanation of how the chemical is named and represented. I only wish my chemistry textbooks had been so straightforward. I'm going to have to bookmark this post, so I can consult it when I want to make sense of some chemical name.

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31. JM on January 30, 2014 12:33 PM writes...

"Sure thing, guys, just like the two component parts of dogwood trees are dogs and wood"

You sir, are a genius

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32. MGlass on January 30, 2014 12:42 PM writes...

Well, chemistry folk, we could really use your expertise on this issue and appreciate you sharing your knowledge. However, before you form your opinions and present them publicly, I suggest you pay attention to what was actually reported as spilled from the Freedom Site. The spilled material consisted MOSTLY of a product called Crude MCHM. This includes MCHM as well as a 1% concentration of methanol. At a minimum, 10,000-gallons of Crude MCHM was released.
As working chemists, you should have to spend little time in locating the Safety Data Sheet for Crude MCHM from Eastman Chemical, which presents the component concentrations.
Again, if you have any informed insight to share, we in WV really appreciate the help.

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33. Nate on January 30, 2014 1:02 PM writes...

If it helps nail a highly negligent company (or shell company) to the wall them I'm all for the fear mongering. They are spinning it that a lot of methanol is in the water, the coal people are claiming MCHM is near harmless and this is not a big deal. It's a propaganda fight and I hope the people win

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34. newnickname on January 30, 2014 1:07 PM writes...

There's some info at ToxNet. Too much to cut and paste, so I'll pick and choose:

Environmental Fate/Exposure Summary:
Methylcyclohexanol's production and use as a solvent for cellulose esters and ethers and for lacquers resins, oils, and waxes, an antioxidant for lubricants, and a blending agent for special textile soaps and detergents may result in its release to the environment through various waste streams. Methylcyclohexanol is a commercial mixture that contains isomers of 2-, 3-, and 4-methylcyclohexanol, which are expected to behave in a similar manner in the environment.

4-Methylcyclohexanol degraded 94.0% during a 5-day screening test using an acclimated sewage inoculum.

Environmental Biodegradation:
AEROBIC: Methylcyclohexanol is a commercial mixture that contains isomers of 2-, 3-, and 4-methylcyclohexanol, which are expected to have behave in a similar manner in the environment(SRC). 4-Methylcyclohexanol degraded 94.0% based on COD removal in a 5-day screening test using an acclimated activated sludge inoculum(1).
[(1) Pitter P; Water Res 10: 231-5 (1976)]


toxnet.nlm.nih.gov /cgi-bin/sis/search /a?dbs+hsdb:@term+@DOCNO+2910

Permalink to Comment

35. Curt F. on January 30, 2014 1:17 PM writes...

@35. newnickname. "4-methylcyclohexanol" is a different compound. It has no CH2 group between the OH and the cyclohexane ring.

Permalink to Comment

36. Pig Farmer on January 30, 2014 1:31 PM writes...

I don't think Derek or anyone else here is trying to make light of this case of criminal negligence. I live in Charleston, WV, and believe me, I am mad as hell about what happened. I want those guys to do jail time. But it doesn't help anyone to make overblown statments about the toxicity of MCHM, or the risk of cancer from the levels of formaldehyde in the water that we are seeing. I am using the water for showering and washing clothes and dishes as normal. I'm not drinking it because it still tastes of industrial solvent, which I don't like. But I am not worried that I'm going to be poisoned or die of cancer down the line because of this. Am I 100% certain of this? Of course not. But I place the risk of death from this chemical way below the risk of, say, being killed in a car accident on the way to work.
To repeat. There is no excuse for what happened, Freedom Industries have lost their right to operate in the area, and the owners should be prosecuted for criminal negligence. But lets not let our justified anger with the owners of this outfit cloud our judgement as to the risks associated with these chemicals. Logic has to be brought to bear on this issue, and that is what Derek is doing here.

Permalink to Comment

37. Anonymous on January 30, 2014 1:31 PM writes...

@14 miralax is made of polyethylene glycol. you have to chug down quite a bit of the stuff for it to achieve the desired effect. i wonder if whatever polyglycol ether was spilled would be any more dangerous (i would naively assume not)

Permalink to Comment

38. Anonymous on January 30, 2014 1:41 PM writes...

"just like the two component parts of dogwood trees are dogs and wood" - LOL, that just cracked me up!

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39. Pig Farmer on January 30, 2014 1:42 PM writes...

And, yes, I've seen the Eastman MSDS and the document that lists the 6 or 7 chemicals that make up crude MCHM, and also the MSDS for PPH, the other chemical involved. I am satisfied that none of them will present me with a serious health hazard. But this doesn't let Freedom Industries of the hook, and I'm certainly not a shill for Big Coal.

Permalink to Comment

40. pete on January 30, 2014 1:55 PM writes...

*rant alert*
Indications are that better regulatory oversight may have easily prevented this spill. But this is WV, where coal is KING and "regulations" is just a dirty word.

Speaking of which. I'm reminded of the fertilizer plant blast in west Texas last year (http://photos.oregonlive.com/photo-essay/2013/04/aerial_photos_of_damage_by_fer.html). In Photo 6 middle/right are the remnants of the fertilizer plant & bottom/center is the heavily damaged middle school; Photo 12 is a closeup of the damaged school. So how, you might ask, would anyone in their right mind permit schools & residences to be located so close to a potentially dangerous factory? I guess it's just how they roll down there.

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41. Anonymous on January 30, 2014 3:53 PM writes...

The oral reference dose for formaldehyde in drinking water is 0.2 mg/kg/day. Source (http://www.epa.gov/iris/subst/0419.htm)

Based on this, a resident of WV that weighs 50 kg should limit their intake of drinking water to less than 333 L of water per day. Just to be on the safe side.

Permalink to Comment

42. gippgig on January 30, 2014 3:56 PM writes...

One of the biggest issues here is that NOONE KNOWS how dangerous MCHM is. Most chemicals have never been tested to determine their health risk. (The Washington Post had an article on this (Gaps are wide in chemical testing, regulation) on Jan. 20.) Running basic tests on the tens of thousands of chemicals in use would be a very worthwhile project.

Permalink to Comment

43. Esteban on January 30, 2014 3:59 PM writes...

This is all very confusing to a non-chemist like myself. I think I'll wait to hear from Jenny McCarthy before I make up my mind. Of course she probably doesn't read this blog. Perhaps Lane Simonian could enlighten us.

Permalink to Comment

44. anoa changa on January 30, 2014 4:15 PM writes...

So did you consider the PPH that was in the tank as well? And are you only looking at pure MCHM or crude MCHM , which is what was spilled in our water supply. As an affected resident I would like to get real answers to what us going on?

Permalink to Comment

45. anoa changa on January 30, 2014 4:16 PM writes...

So did you consider the PPH that was in the tank as well? And are you only looking at pure MCHM or crude MCHM , which is what was spilled in our water supply. As an affected resident I would like to get real answers to what us going on?

Permalink to Comment

46. Tom on January 30, 2014 4:29 PM writes...

We're having a water contamination issue here in NJ... a local industry, Solvay Solexis, works with PFC's and unfortunately, contaminated the groundwater. Specifically, our water has found PFNA at 150 parts per trillion in our main well.

What do you guys know about PFC/PFNA's?

Permalink to Comment

47. John Wayne on January 30, 2014 4:34 PM writes...

I'd like to present a probable outline of the situation:

(1) There was a chemical spell
(2) This chemical spill entered the environment
(3) The plaintiff's want that not to happen again and the company to be fined/punished/etc.

I'm not a lawyer, but it seems like they are asking two questions:
Question 1: Was the company negligent, or is this an accident?
Question 2: Was anybody harmed by the spill?

Question 1 is relatively straightforward, involves investigation, may lead to fines for the company and there might be some regulatory changes in the future.

Question 2 is the tricky one; the greater the perceived loss or damage, the greater the criminal and financial penalty. The plaintiff wants there to be horrible damage, and the defendant wants the damage to be minimal. This is the point where any sort of consensus on the truth leaves us.

Are you willing to pretend that the environmental and health damage was higher than it probably is to punish somebody? Are you not willing to accept other perspectives? Dangerous ground.

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48. Pig Farmer on January 30, 2014 4:36 PM writes...

All of the chemicals in the crude MCHM (with the exception of the 1% methanol) are structurally related to MCHM, and so the arguments used to justify classifying MCHM as only moderately hazardous apply to them too. PPH has a different structure, but similar considerations lead to the conclusion that it too is probably only moderately hazardous. As with all chemicals, the dose makes the poison. The levels of MCHM and PPH are now at sub-ppb levels, so they are very unlikely to cause serious health problems. As with everything, there is no 100% certainty on this, but we all have to live with risk every day (what annoys me about this case though is that the people taking the risk (us) and the people reaping the benefits (Freedom Industries) are different sets of people).
Yes, it would be great to have more data on all these compounds, but toxicity studies are very expensive. How much of an increase in your taxes would you be prepared to pay to fund these studies? Freedom Industries isn't going to pay for them, nor, presumably, is Eastman.

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49. Anonymous 2 on January 30, 2014 4:36 PM writes...

Very informative and a explanation for those of not familiar with chemistry. I'm from Charleston, WV and noticed the chemist from MU said the chemical would stick to plastic pipes and therefore that is why the smell is still in many homes. Is there a way to explain how this chemical breaks down in the water and/or could be sticking to plumbing inside our homes? Is there any way to calculate how long the chemical and smell will remain from a chemistry point of view? Thank you for the breakdown.

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50. Pig Farmer on January 30, 2014 4:46 PM writes...

The chemical will probably be slowly metabolised to a carboxylic acid by water-borne bacteria. The chemical is only moderately miscible with water, and forms a film which floats on the surface. When it encounters plastic it will tend to stick to it. I live in Charleston WV too. I anticipate it will be a matter of weeks before the smell can no longer be detected. The level needs to get below about 0.5 parts per billion before you are no longer able to smell it.

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51. Anonymous on January 30, 2014 4:54 PM writes...

@49

Every molecule has a different tendency to prefer water or oil (hydrophilic versus lipophilic) sometimes referred to as lipophilicity, LogD, partition coefficient, etc. all with slightly different definitions. If this molecule is lipophilic, it would rather associate with something like plastic pipes than with the water, hence why it would tend to accumulate on plastic pipes, soil, and things of that nature, rather than simply dissolve into and travel with the water. It appears that this molecule is indeed quite lipophilic, based on a quick bit of searching and also as the structure would indicate (lots of carbons, very little heteroatoms.)

To remove a lipophilic molecule from plastic, you'd want to use a detergent (hard to do in your plumbing) or you'd simply have to flush a LOT with clean uncontaminated water, as eventually it will be carried away with what little solubility it does have in water.

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52. Patrick Sweetman on January 30, 2014 4:59 PM writes...

#49, yes, given decent estimates of
1. the partition coefficient between water & plastic
2. the initial concentration and time of contact
3. flow rate of the water
4. level of detectability

somebody with a bit of math ability could answer your question. Any takers?

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53. Anonymous on January 30, 2014 5:30 PM writes...

The oral reference dose for formaldehyde in drinking water is 0.2 mg/kg/day. Source (http://www.epa.gov/iris/subst/0419.htm)

Based on this, a resident of WV that weighs 50 kg should limit their intake of drinking water to less than 333 L of water per day. Just to be on the safe side.

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54. MTK on January 30, 2014 5:35 PM writes...

1% methanol.

So a 10,000 gallon spill is 100 gallons of methanol.

The Elk River is currently running at around 740 cubic ft/sec, about 20 miles upstream from the site of spill, but let's use that number. That's 5500 gallons/sec.

Let's that the spill took one hour, which is probably way to short since it was a one-inch hole and that the crude MCHM first leaked into the ground then seeped into the Elk River. That's 20 million gallons of water that went by as the 100 gallons of MeOH contaminated the river. That's 5 ppm of MeOH if my math is correct. Now how much of the MeOH oxidized to formaldehyde. I'm guessing it's pretty darn small.

All in all I'd say that the amount of formaldehyde in the water attributable to the spill is nothing. That's not to minimize the spill itself or its potential consequences, but just to say any argument involving formaldehyde, even if one considers the 1% methanol in crude MCHM doesn't hold (or contaminate) water either.

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55. gippgig on January 30, 2014 5:37 PM writes...

#48: "...toxicity studies are very expensive" - detailed studies are, but basic stuff (expose a tissue culture to different concentrations & then examine under a microscope or with a gene expression chip, Ames test, etc.) should be fairly cheap and easy to do (admittedly doing it for tens of thousands of compounds wouldn't be so cheap or easy but you could start with the most commonly used or least studied ones). If 1000 colleges each tested 10 compounds a year it would get the job done in less than a decade.

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56. LabMan on January 30, 2014 6:51 PM writes...

I knew this would get crazy as soon as I heard Scott make his statements. While this has been a terrible incident, these type of comments are not helping anyone. The amount of formaldehyde found was approximately 33 ppb, the typical amount found in toilets with city water all over the country. Check the sample ID on his sample and this issue can be closed.

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57. Lab Rat on January 30, 2014 7:18 PM writes...

For the commenters with chemistry knowledge...can you recommend a cost effective and reliable lab, or some such service, where a Charleston, WV resident (that be me) could send their tap water for testing?

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58. gippgig on January 30, 2014 7:40 PM writes...

#59: Check if any local university labs would do it.

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59. DrDeb on January 30, 2014 8:26 PM writes...

What is the chemical name for PPH?

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60. Batam on January 30, 2014 8:34 PM writes...

How would these chemicals react with chlorine or other chemicals used in water purification?

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61. Luke Weston on January 30, 2014 8:35 PM writes...

If you go and do basic lab tests like Ames on millions of common chemicals around us in the environment every day you find that many if not most of them are actually horrible scary mutagenic carcinogenic evil and then they need to be banned in California.

That's why it's not viable to just do this sort of basic testing on everything - it doesn't tell us a damn thing about epidemiology, about any real effect on public health, but it will benefit lawyers, quacks like Mercola, and the industry that has sprung up around things like Prop 65 because you could use it to falsely claim every single compound as a public health menace.

And these aren't just the synthetic products manufactured by Big Evil Monsanto or Big Evil CoalCorp, most of these chemicals around us are the color of a flower, or the taste of a banana, the aroma of a cup of coffee.

There are at least 1000 different chemicals in ordinary, natural coffee beans. Only about 30 of those have been subjected to basic toxicology studies in the lab - stuff like Ames, or force feeding it to rats until they can't withstand any more, etc.

And of those 30, 20 are carcinogenic in the animal studies. Two thirds of those compounds tested.

What about the other 970 compounds? We don't know. They haven't done the testing! They don't want you to know! We've got absolutely no idea if it's safe or not!

:)

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62. Actually on January 30, 2014 8:35 PM writes...

Actually, it was a four foot spill hole. DEP inspectors found the "secondary" containment dyke with a four foot stream coming out and for good measure a Freedom Industries staff member had put a bag of absorbent kitty liter in front of the massively cracked masonry. The "1 inch hole" was a fable by Freedom Industries President to try and downplay the spill in the first 48 hours. He also said only 2500 -5,000 gallons was spilled - that's now been upped to at least 10,000 gallons and a second chemical added to the spill. I'm sure more info will trickle out at a much slower pace than the MCHM did into the Elk River.

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63. Nick K on January 30, 2014 10:12 PM writes...

#19 Curt F: I, too, would like to know the answer to your question. I really hate the modern system of nomenclature, such as "benzenemethanol" for benzyl alcohol and "benzeneamine" for aniline.

This idiotic panic about formaldehyde would probably never have occurred if the spilled compound had been named according to the old system.

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64. Really on January 30, 2014 10:26 PM writes...

A tragedy of this sort hurts the people and the community, the only winner is the lawyer. Why else would they file claims the day after the accident and spend fortunes on commercials to entice us that they are going to help us. Freedom should pay and be held responsible. Whatever money or insurance they have should go to the govt agencies that the tax payers own and have spent millions on cleanup. Suing the water co hurts all. We have to have them. We each get $10 for a multimillion suit and a handful of lawyers get millions then rates go up and we end up paying the tab.

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65. MoMo on January 30, 2014 10:36 PM writes...

Who cares about methanol when the primary alcohol is metabolized to the aldehyde? The damaging compound is the lipophilic 4-methylcyclohexane carboxaldehyde. That 's the Phase I metabolite I would worry about in vivo , in situ, ad nauseum ad infinitum!

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66. Anonymous BMS Researcher on January 30, 2014 11:08 PM writes...

Much nonsense has been said about formaldehyde, in particular some people claim the sweetener aspartame is dangerous because it gets metabolized to formaldehyde. However, the amount of formaldehyde you'd get from a cup of orange juice, or a bowl of tomato soup, or a can of beer is orders of magnitude more than you'd get from consuming a product sweetened with aspartame.

The truth is, we ingest thousands of natural toxins every day, nearly all plants make small amounts of toxins. Our bodies can handle modest amounts of toxins very well indeed. I've been at MANY a Discovery Working Group Meeting where the main subject of discussion has been the difficulty of preventing our compounds from getting metabolized too quickly; I know Derek has been part of similar conversations at his company. Anybody who has worked in Drug Discovery knows mammalian bodies are darned good at ripping apart strange molecules.

And one of the most toxic substances in our environment is -- roll of drums -- OXYGEN. O2 is very reactive; a significant part of our cellular biochemical machinery is devoted to repairing the damage done by oxygen. Of course without oxygen I'd soon be dead.

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67. Matthew on January 30, 2014 11:24 PM writes...

I've had enough Chem and Bio in college to understand the basics of what you've said, I also understand the comparison of tomato levels vs the levels in the water. The point I'd like to ask though is a matter of volume. How many tomato's can a person consume in a day before it's toxic? Considering that the average Human should consume more water than they do tomato's and on a more consistent basis as well as bath and washing hands I'd going to say that even though the exposure is only a little higher than a tomato the rate of exposure is much higher simply because of the reasons stated above. Now is this harmful I'm uncertain since I'm not versed in chemistry enough to understand or formulate a methodology as to measure the toxicity from consumption. Although studies vary 3 liters is suggested for men, less for women. Add in consumption from cooking (While may break down the chemical when heat is added?) and on top of that bathing etc etc. Do you see this as a concern? I mean that's a bucket of tomato's to chow down on and chow down on a daily basis I'm guessing since exposure is measure not only in the amount taken into the body but how long the body is exposed.

It was stated 1mg/mL is in the human body at any given time, and the levels in the water were around 27ng/mL I believe. How about exposure to the young or elderly? I'm like you and believe it's a lot of hype I suspect which will be used to add ammo the the EPA in it's onslaught to impose new laws. I doubt that storage site would have been built there if it was built in the last 10 years but it was built in the 50's when city planning wasn't exactly top notch in the area I imagine lol.

Using EPA data they measure in Meters Cubed so since my conversion skills suck if anyone is interested here is the link to the EPA data.

http://www.epa.gov/ttn/atw/hlthef/formalde.html

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68. Fred G on January 31, 2014 12:13 AM writes...

Just wondering: What happens when chlorine is mixed with the 4-methylcyclohexanemethanol at the water treatment plant? There are so many other things that are/ could be in the water in the Charleston area- what would have to be present to produce the claimed formaldehyde?

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69. gippgig on January 31, 2014 1:29 AM writes...

Chlorine could react slowly with MCHM but the levels of each are so low that the amount of reaction products should be far too low to be significant.
By the way, is methylcyclohexane "dangerous and toxic"?

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70. JR on January 31, 2014 7:06 AM writes...

Thank you Derek.. We have become a country that excepts everything that Government and the mainstream media tell us. It's uplifting to see people like yourself, who decide to research and form their own opinion. The more and more I discover and hear about this spill, the less and less it adds up. I mean, have you ever heard of a company being open for 9 days and showing this type of negligence? Not to mention all of the inconsistencies, such as this. I do remember a certain some one declaring a war on Coal, back in 2009. If you look at how the Owner conducted his first interview, the rude comments from the other owner's girlfriend and not to mention, MSNBC made sure that we all knew these jerks filed for bankruptcy and then used a loophole to become the owners again. MSNBC was NO where to be found when the spill first happened, because they were covering the Bridge Scandal and pushing their Agenda. Obama knows the people of WV love their Coal and to put a whole state out of work, would make him look even more heartless than he already is( IF that's possible). So how does he win the war on coal? He wins by turning the people against the very industry they love and are all so proud of. Sad thing is that it's working. I have been seeing people with I support water stickers, screaming for regulations and basically siding with this guy. WE don't need more regulations, we need to redo the whole checks and balances part from scratch. Starting this process by never allowing a company to go 20 years, without being inspected. Then we shut down the loopholes that allow the rich to get of Scott free. These are things we can make our state legislatures do and they keep King OBAMA away from from our great state. I may sound like a conspiracy theorist, but until someone can tell me the last honest thing Obama has done, I'll trust my gut!!

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71. Anon on January 31, 2014 7:29 AM writes...

JR - keep trusting your gut. Before that, think about some of the statements you have made. "We don't need new regulations, we need to redo the whole checks.....Starting this process by never allowing a company to go 20 years, without being inspected". FYI, that itself is a new regulation.

So now any accident that happens is due to deliberate action by Obama? Just how f*&^ing stupid are you? MSNBC is pushing their agenda? Betcha that you think that fox is "fair and balanced" too. Get out of your mother's basement, learn some proper English and try reading different points of view. Let go of the gun and the bible once in a while. It is refreshing.

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72. toJR on January 31, 2014 7:51 AM writes...

Hi, JR

If you read what Derek actually wrote, he's referring specifically to the formaldehyde claim. The chemical spill is something that really should not have happened and happened because this company chose to be negligent. There's no need for conspiracy. Accidents happen, and sometimes they ruin the lives of thousands.

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73. Brad Means on January 31, 2014 8:24 AM writes...

The Spring Hill cemetery has been on the hill above the water co for 130 years , any dirt dug up is confined to the cemetery because of its high content of formaldehyde , any dirt dug up is dumped over the hill on the elk river side ! could the runoff from the cemetery be a factor if infact there is formaldehyde in the elk river ? and should this be tested for ?

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74. MTK on January 31, 2014 9:15 AM writes...

@62,

I'm not sure why you put "secondary" in quotes, but in any event a four feet hole or breech in secondary containment, does not preclude a one-inch hole in primary containment. If that's the case then the 1 inch hole is still the rate limiting factor in terms of how fast the spill seeped into the ground and eventually into the river.

The point is that even if you look at something close to worse case scenarios, the amount of formaldehyde attributable to the spill is almost nothing and certainly far less than any known hazardous level.

Once again that's not to minimize the effects of the spill as a whole since over 90% of the material of MCHM. But that's the point. Instead of worrying about the mote (formaldehyde) one instead should be worrying about the beam (MCHM).

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75. John on January 31, 2014 10:22 AM writes...

Great read and great blog. Love the insight into the average citizen’s science illiteracy. My fiancé (atmospheric science educated nerd) always gets beyond livid at news reporting and the incorrect use of terms. The best part about the reporting is the sensationalism of a measuring system Americans don’t use in everyday life. 30 ng/ml!? WHAT IS THAT?! That MUST be a like a pound or something. Dr. NdGT mentioned something similar from a cocaine trial where the defendant was accused of having 1,700 mg of cocaine. 1,700 mg!? MOTHER OF GOD. WAS THIS GUY SUPPLYING SCARFACE? (In reality, convention would usually call this 1.7, which is about the weight of a dime.)

Just funny. People just don’t want to ask questions or do their own research from credible academic sources.

BTW—I know I’m not the only one out there—Did anyone else get excited when they heard the chemical and drew it correctly? I live in WV so I’m not saying I was excited for pollution, but you bet your ass I was excited my complete undergraduate degree wasn’t a waste.. at least in drawing obscure organic molecules.

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76. Al Justice on January 31, 2014 10:37 AM writes...

The coal cleaning chemical spill should not have happened. Sad.

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77. WV home on January 31, 2014 10:49 AM writes...

Derek,
If you could speak specifically about the chemical that was spiled and what the cancer and health issues this will cause the citizens of WV that have to drink, cook, bath because the state is not willing to provide clean water !!

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78. cynical1 on January 31, 2014 12:06 PM writes...

@pigfarmer. According to you, MCHM has a odor threshold of 0.5 ppb. And a quick Google search from public sources (in WV) that were reporting the spill say that it can be as low as 0.2 ppb.

So, here's the thing, I actually am a chemist and I looked up the odor threshold of methane thiol. That's the tiny amount of gas (not liquid) they add to natural gas to let you know you have a gas leak because it's pretty much odorless otherwise. The odor threshold according to a CDC document I read was listed as 1 ppb. And I've used that stuff and when I condensed it out of the cylinder, the whole building knew it and I was doing everything humanly possible to contain the odor.

So do any other chemists out there have a hard time believing a molecule with that structure has an odor threshold that low. Because, if it did, you should have been able to smell the containment facility at Freedom Industries for many, many miles around it without any massive leak. I didn't get the impression that they were using vacuum sealed containment. And any industrial use of that chemical in the coal industry on the scale that would have generated that much waste would have stunk up the air for many, many, many miles away. I'm surprised that I didn't smell it where I live, a few states away. I was using 1-phenylethanol yesterday and that's pretty damn close in MW and structure to MCHM. I caught a whiff of it when I was weighing it out but I'll tell you that I was getting much more than 1 ppb up my snot hole too. (I want to make the MCHM analog in my series just so I can see just how pungent that stuff really is. Though I will admit that it wasn't originally in the list of alcohols I ordered but I think I could justify it, especially if the phenethyl analog is active.....) So, I certainly could be wrong but I have to admit having a hard time believing the 0.5 ppb odor threshold.

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79. Limond on January 31, 2014 12:19 PM writes...

Thank you for nothing. It seems really interesting you chose to pounce on an opportunity to downplay this chemical spill. I would love to hear you opinion on the methodology for how they came up with the 1 ppm safe level of pure MCHM, as well as how the polyglycol ethers are nothing to worry about. I guess if one were interested in contemplating making methanol from pure MCHM this blog post would be worth reading, or wanted to understand the basic chemical language used by chemists and biochemists. It is clear as day you are only a chemist and have limited knowledge in how chemistry occurs in the context of a biological organism. Furthermore, if indeed he did find formaldehyde at 30 ppb, that is 3 times the recommended level in drinking water suggested by the CDC (10 ppb over 10 days). Is that not significant? Would you drink water that was 3 times over the recommended limit for over 10 days? You also ignore the fact 10,000 gallons is a unit of volume and not a unit of concentration. As a chemist you should know this is what really matters, yet you don't ever consider this? 1 ppm of formaldehyde is not the same number of molecules as 1 ppm of MCHM...come on man, use your knowledge to help not distract.

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80. Russ McDaniel on January 31, 2014 12:21 PM writes...

Question concerning the group. What is the difference between CH3OH and CH2OH?

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81. Anonymous on January 31, 2014 1:09 PM writes...

The first one is methanol and the second one is something an organic chemist would attach to a molecule called a hydroxymethyl functional group. In the case of MCHM, it is attached to methylcyclohexane. To a lawyer, it's all the same.

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82. Tim from SA on January 31, 2014 1:34 PM writes...

Derek – Thanks for the article, a friend sent me the link, first time reader.
I know I’m not the only chemist in the Kanawha Valley that took calls from friends and family about what this stuff is and what will it do. Mostly I tried to calm fears and carry on. I did not change my behavior much during the spill. And told my mom, who was deathly worried, that 30 times a day she inhales more known carcinogens voluntarily by smoking than she will ever get drinking the water. Another case of not understanding risk.
First about formaldehyde – The lawyers need to find a known, proven carcinogen in the water to make a case. Otherwise they will have to provide data the mixture/by-products/chlorine and fluorine products, metabolic derivatives, etc. cause the effects the people have claimed. Which will be a challenge. It is much easier to sell a known carcinogen to a jury. They don’t need to prove cause and effect in that scenario – boatloads of data on the knowns.
The lawsuits for business loss are easy to prove, that is why most lawyer adds focus on them.
Personally I am going to claim damages for all the Bisphenol A I was exposed to from having to drink bottled water.

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83. Atty on January 31, 2014 2:21 PM writes...

You know your chemical formulas, and I believe you. However, you do need to figure out which side of a lawsuit is the plaintiff, and which side is the defendant. For future reference, the plaintiff(s) come first (usually on top of the v.), since they are complaining, against the "defendants" who are named second. Vandalia and its owners are plaintiffs. Not defendants.

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84. Chaleston Charlie on January 31, 2014 3:37 PM writes...

All this brain power to decipher Formaldehyde, yet little or no assistance on how to remedy the problem...The citizens of Charleston applaud you for your assistance in helping with a crisis.
We all should start teaching our kids to take down a fellow American to make yourself look good. I see it gets you far in this country.

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85. Charleston Charlie on January 31, 2014 3:38 PM writes...

All this brain power to decipher Formaldehyde, yet little or no assistance on how to remedy the problem...The citizens of Charleston applaud you for your assistance in helping with a crisis.
We all should start teaching our kids to take down a fellow American to make yourself look good. I see it gets you far in this country.

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86. MTK on January 31, 2014 4:02 PM writes...

@85,

Get off your high moralizing horse.

If you would actually think through it a little, we are assisting by pointing out that the whole formaldehyde issue is a canard. It's nonsense which is actually taking attention away from risks that could actually be real.

A good cause is harmed by a bad argument which is exactly what is going on here. There is no reasonable expectation that the formaldehyde level observed here was due to the spill based on either the chemicals involved or the amount spilled.

In addition, the amount of formaldehyde found in the water at the restaurant is "commonly encountered" according to Dr. Vikas Kapil, a CDC senior medical officer. If that's the case, then without knowing the formaldehyde levels in the water prior to the spill it's impossible to know what contribution the spill may have made, even if it were chemically possible.

Real harm has been done here by this spill, but that real harm is being obscured by this BS. Think about it. If this goes to court and the plaintiffs bring this crap up, the defense's expert witness shreds it and that jeopardizes the entire lawsuit regardless of its merits based on other lines of evidence.

So no, it's not trying to take down a fellow American, it's taking down a flawed argument. And it is assisting by trying to keep the issues on point rather than off-base.

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87. Anon on January 31, 2014 4:30 PM writes...

#85: "Take down a fellow American"

Shades of Tea Party faux patriotism are echoing in that statement.

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88. Rich McG on January 31, 2014 4:30 PM writes...

I read Derek's column and am in agreement with the chemical end of it. I was able to read it because one of my Republican Facebook friends that likes to discount any theory that anyone is trying to get any type of handout, money from litigation, etc., is evil.

I'm glad I got to read it because it was easy to discount, and I said as much on his facebook post. While Derek is correct on the math, he may be wrong on so many other levels.

I too noticed the Defendant's vs. Plaintiff's issue. But I'm a biologist turned lawyer. That's not the problem, and it's simple mistake. It's a blog people. Derek's not a lawyer, and he clearly doesn't have all the facts.

So I too applaud him for posting a good chemical analysis of the main component of the spill.

But here's the problem - he doesn't have the complete picture.

First, as has been discussed herein, it was crude MCHM, which contains 6 or 7 other chemicals, including 1% methanol. So we don't have to get formaldehyde from MCHM, we can get it from the methanol.

Second, I stand among those who question whether methanol was present in enough concentration to bilogically degrade and give us enough formaldehyde to form a cancer risk, and I understand that I am probably at more risk from second hand smoke, but I avoid THAT too!

Dr. Simonton did not say we are at danger from drinking the water. He said he was concerned about the gaseous phase. There is a difference.

Further, everyone is assumiung the company is telling the truth, as is the government. Nothing in this entire scenario presents any facts that lead us to have ANY trust whatsoever in the government.

I drank the water, day one, before it was known. My daughter, 5, bathed in the water, and was complaining about "my whole body itching" for several days before we knew about the leak. That has never happened before. Of course, she likes her baths, adn stays in for a friggin hour sometimes til I have to drag her out. I showered, my eyes burned for 3-4 hours after. I felt naseaous that evening, and even had a dizzy spell. I haven't sued anyone yet, and may never join any suit. I am a realist.

But I am a realist that is appaled by what has transpired.

Don't focus on a 1 inch hole. The tanks are set back approximately 20-30 feet from the river, behind an extremely aged, concrete block wall about 4 feet high, and partly surrounded by concrete and gravel. There was no magical "one inch hole" that leaked directly into the water, to where you can use some flow rate and any calculation to even ballpark a known ppm or ppb. When the inspectors showed up they documented a 4 foot wide stream of this stuff flowing towards the concrete block wall and disappearing not through the wall, but into a crack along the bottom of it. Photos of the site showed a stream of liquid flowing from directly below the tank that leaked down 20-25 feet into the river. There was not any drainage pipes anywhere near there, or drainage through the wall that would account for that stream being anything but crude MCHM. It was also not raining.

The company floated many theories in the days after the indicent. What did not flow were real facts, or the truth.

What started as 2000 gallons became 2000-4000, then 4000, then 5000, then 7500. Then we were told TWENTY days after the reporting of the leak (and I don't say leak starting because it didn't start on January 9th, it was reported January 9th), that there was a proprietary, secret formula chemical called PPH in the water. Never fear the state and Freedumb Industries tells us, it's bad, but it's not as bad a chemical as MCHM, trust us.

So we don't really know how much leaked. The tank farm was built in the 40s or 50s as a Pennzoil oil storage facility. These bozos bought it in 1991. One of the original incorporators has already gone to prison for tax evasion from activities around THAT tank farm, and for dealing cocaine (Trust these folks yet). The guy they stuck on air, the former president (the guy who was listed as THE president on the website the DAY of the leak, and I think still is), owns a biker bar outside town and a restaurant that has been terribly inconsistent from my experiences there (rumor is he was still operating the bar/restaurant during the ban). His girlfriend reported on her Facebook that the "President," Gary Southern, that we were seeing on TV drinking bottled water, was a PR guy that the company brought in. Gary Southern apparently has a long history as a chemical salesman. He did a pretty bad job selling this snake oil.

As also noted herein, 9 days before the leak was "discovered" the company mysteriously changed hands. Can you smell a hide-the-money coverup yet? Either the new owner, a coal baron type from neighboring PA, who had NEVER had an interest in ANY WV business, suddently has this problem. Starts another company, puts this one into bankruptcy, uses the other new company to try to loan this company bankruptcy to continue operations and try to shield itself from these bad actors/bad actions. Remains to be seen if any of that will work. Criminal charges should follow, and the US Attorney on the case, Booth Goodwin, is a good one, who has recently taken down both judges and politicians, and isn't going to shy away from these bozos.

Why do I spout all this? Back to my point, we don't know how much was spilled, we don't know how much was methanol. We don't know how much was MCHM. We don't know what else was in those tanks. And ALL of the bozos that they had up there in front of the microphones were the same bozos, public and private, that got us into this mess to begin with. So we should trust them?

Back to my points:

How much was spilled. No one knows. ALL the estimates have been based on the company numbers. There are NO independent verifications of anything yet. I'm assuming, and hoping, that our US Attorney is all over that. I would want to see invoices going back a LONG time. These tanks are rusty and decrepit looking in every photo and from every angle.

Secondly, what was spilled. The tank says Crude MCHM. We now know the company used 6% PPH (They say 6%). Someone herein has indicated crude MCHM may be expensive. So a company of criminal bozos like this wouldn't tinker with the mixture a little to make it cheaper? More methanol? Is methanol cheaper than MCHM. I don't know. I would maybe bet money it is.

Why hasn't anyone tested what was actually IN the tank? The allegedly moves 100K gallons of this stuff out of the 3 tanks there that held it (there wasn't just ONE tank of MCHM, but 3). The tank farm has 13 to 15 tanks, with a reported capacity of 4 million gallons, anyone test any of the other tanks? What's in them, for leaks?

It's the blind leading the blind here folks.

I haven't seen any PPH testing done either.

Seriously, this is a comedic comedy of errors the way I see it all the way around.

And now we have a DHHR PhD, (what's HER PhD in?), calling Dr. Simonton, who merely reported he found formaldehyde in the taps, and would be concerned if people were INHALING it. They call him irresponsible. This is a DHHR PhD from the same agency, DHHR, who refused to adopt the recommendation of the Federal Chemical Safety Review Board after Bayer blew up a tank and two employees in 2011, because they "didn't have anyone on staff to write the plans." So they sent it back to the legislature for review. What happened then? Nothing.

So we are supposed to trust these folks, charged with the public health, who refuse to regulate, who refuse to do testing, and they are going to call out people who are actually trying to get facts?

I trust your chemistry Derek. I also trust that you don't know all the facts here.

I stand with the other science educated folks here in not wanting to jump to conclusions as to the seriousness of the health threat this poses to us. But I also stand as an attorney who has sued coal companies, sued DEP, who has been in DEP offices reviewing permit files and was appaled by what he found (for example, classifying someone as a soil expert, a mining engineering graduate, because he took one class in agronomy as an undergrad). I stand among the citizens here, intelligent ones, who want to know what's in my water, and who won't trust what the bozos that got us into this mess are telling us.

I also am not comforted by the same bozos sitting up there a table drinking tap water (if that's truly what it is). Again, these bozos were stupid enough to get us into this mess, I fully believe they are stupid enough to drink their own Kool Aid.

So what do we know? We know that the formaldehyde isn't coming directly from the chemical MCHM; that it MAY be coming from the methanol; that we don't know if there's enough to hurt us; that we don't know really what's in the water; and that there are a lot of bad actors here that need punished.

I'm still not drinking the water. And I'm keeping my 5 year old away from it too.

Cheers.

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89. Charleston Charlie on January 31, 2014 4:43 PM writes...

Look. There is a crisis going on in Charleston Folks. After hours of flushing my water it still stinks. My clothes itch from washing in this crude while rashes, nose bleeds and headaches are still being encountered. This isn't a definitive argument. Peoples lives are on the line here. You all are the chemists; tell us something that can dissipate this. Not about money making ploys by lawyers

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90. Another Chemist on January 31, 2014 7:34 PM writes...

Charleston Charlie @94
Unfortunately, I wouldn't expect enough is known about the physical (and perhaps even chemical) properties of MCHM to formulate a methodology to purge what's still in the supply line in short order. The situation is even more complicated since we are dealing with a mixture of organics.


I live in Cross Lanes and my water still stinks somewhat (not to mention having a new metallic taste), so yeah, my family is still drinking and cooking with water from other sources than WVAW. Interestingly enough, I don't notice the stink or taste at my workplace in So. Chas. And, by the way, the plumbing in my house is copper with a trivial amount of steel, not plastic, all the way from the water meter to the furthest shower head.

I started taking real showers again 4 days after the spill was announced. My decision was based solely on expediency and I will accept whatever consequences come to pass. My wife and daughter never really stopped showering in the tainted water. None of us have suffered any bad reactions (to date). My wife even claims her psoriasis is retreating a bit (likely coincidence). However, the spike in skin rashes and other ill effects reported in the area recently IS too large to ignore. The obvious conclusion is that those of us exposed have different sensitivities to the various organics involved, or that there has been a bubble of psychosomatic reaction (which I don't really believe!).

Sadly, we don't know all the physical details of the leak/spill and may never. We can build models all day long (and should). But we shouldn't forget what George Box--a notoriously good statistician who died last year--is attributed to have said. To paraphrase: all models are wrong, but some are useful.

Finally, my personal opinion is that the formaldehyde recently found in the water is a red hearing probably unrelated to the MCHM spill and likely there all along.

I'd like to thank Derek, Pig Farmer, MTK, Rich McG and several other for a well-reasoned blog and great comments.

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91. Stacy on January 31, 2014 7:37 PM writes...

Derek,

I appreciated your article for the science it explained. I live in Charleston, WV and whether it's 4-mchm, or methanol or whatever, I'm no longer drinking the water. The "science" provided by the Governor's office and the water company has been lacking too. I also want to be clear that you weren't trying to make the law firm Thompson and Barney look like idiots.

Here in Charleston, these guys are the good guys. They're not fear mongering. They're the type of firm that represents families in WV who can't get access to their family's cemeteries when the coal companies come in and privatize the access roads and don't let them on without being harangued. They represent whole communities whose water has been poisoned by coal slurry when all the well water goes bad.

In fact, they'd probably be interested in hearing your assessment and in knowing that they may have gotten a detail wrong in their case as you have noted.

As far as I know they're the only firm that's even tried to do their own assessment of the water - when the water company and government refuse to test the faucets here.

Anyway, just sayin' the law suits filed by Thompson and Barney aren't a money making ploy. They're not scumbag lawyers trying to exploit a really really bad situation. They're the good guys.

I kind of wish instead you were critisizing the "science" of the industries trying to shove down our throats that the water with 4-MCHM is safe for human consumption.

The post kind of touched a nerve.

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92. Another Chemist on January 31, 2014 8:04 PM writes...

A couple of follow-on responses...

Lab Rat @57
I have heard Triad Engineering will analyze water samples for MCHM. Can't confirm, nor do I know the cost.

DrDeb @59
PPH is propylene glycol phenyl ether (AKA 1-phenoxy 2-propanol). One manufacturer (only?), coincidentally, is Dow, but probably not at WV operations. Dow calls it DOWANOL PPH Glycol Ether and an informative MSDS and Product Safety Assessment are available on the Dow website.

The additive in Freedom's MCHM tanks was billed as PPH-stripped. I'm not certain exactly what "stripped" means in this case, but it suggests light ends (low-boiling trace compounds) were removed.

PPH is certainly in the same chemical family as diethyl ether (mentioned somewhere, I think), but is a far cry from being diethyl ether.

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93. gippgig on February 1, 2014 2:22 AM writes...

PPH is somewhat similar to guaifenesin, found in cough syrups like Mucinex (which doesn't prove anything).

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94. Mary-Jacq on February 1, 2014 5:42 AM writes...

The samples were taken in a restaurant which has commercial ovens that operate up to 800F and commercial dish/utensil cleaners which operate at temperatures and under pressure like an autoclave. These devices could be acting as cracking furnaces adding pressure as well as elevated temperatures that would completely change the chemical balance and resultant products.

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95. Anonymous BMS Researcher on February 1, 2014 9:04 AM writes...


This academic has started a crowdfunding campaign to raise money for independent research on the spill:

http://www.southce.org/ajwhelton/

He and his students have already made one trip there on their own time and money.

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96. metaphysician on February 1, 2014 9:07 AM writes...

So, I'm going to ask the blunt question people seem too polite to ask: 'Do we have any reason to believe that the reports of rashes and such is anything other than the placebo effect?' Because those sound like exactly the kind of vague symptoms people would report when they think they have been exposed to something toxic.

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97. Anonymous BMS Researcher on February 1, 2014 9:22 AM writes...

@metaphysician: Google NOCEBO EFFECT

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98. Anonymous BMS Researcher on February 1, 2014 10:15 AM writes...

As for methanol: every filling station I have ever seen has plastic bottles of windshield washer fluid. Usually this stuff consists mainly of water and methanol, sometimes also ethanol, sometimes other additives such as glycols or surfactants, and usually blue dye. Almost certainly the amount of methanol sprayed into the WV environment by people's cars exceeds the amount of MEOH in the spill.

Yes the spill was awful. Whether or not the solvent has caused medical harm -- and I doubt anybody has good data on that yet -- clearly this disaster has already caused enormous economic and social harm for which those responsible ought to be held accountable.

I hope some Foundation with deep pockets will fund transparent, independent, high-quality research as soon as possible: the need for trustworthy data appears to be huge. If I lived in the affected area, I would trust neither anybody connected to lawyers nor anybody with ties to the coal industry. Sadly, I expect few domain experts in WV have ties to neither the Tort Bar nor Big Coal.

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99. digger on February 1, 2014 5:31 PM writes...

I understand that very toxic materials are being spread daily n the highways so peopple can travel. Sodium and chlorine are both deadly. Wonder what a ground swell that would cause if presented by a journalist who was after sensationalism and worded it in a manner to hide that it is table salt?

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100. John on February 1, 2014 8:23 PM writes...

Has anyone thought that the solvent could have leached something else out of the site soil or river sediment? The thing that is really causing itches and hurting eyes could have been spilled into the river or on site many years ago. The problem could be cause the people treating the water thought it smelled funny and added more chlorine than normal and that can cause all the problems people are up in arms about.

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101. Catherine on February 1, 2014 10:04 PM writes...

I live in Charleston also...i knew from the very day of the spill that there would be law suits out the yazoo...its typical in the me hungry society we have today...my concern has been about the crude mchm and pph mixture being doused with the chlorinated chemicals in the water treatment plant...msds sheets that i have seen clearly stated that oxidizing agents and crude mchm did not get along very well...IF in a panic and the treatment plant dumped more than usual "chlorine" (since i am not sure exactly what they use} what reaction occurs and how dangerous was THAT during the initial stages...do you have any info on that? ... i just want to get to the truth about this chemical mess so i can feel more comfortable

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102. chemophobic on February 2, 2014 3:25 PM writes...

If only they used chemical free solvents to clean the coal we would not be having this discussion...

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103. Cymantrene on February 5, 2014 3:25 AM writes...

@chemofobic: water itself _is_ a chemical. Used in huge scales in chemical industry. Just like air.

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104. chemophobic on February 5, 2014 10:31 AM writes...

@Cymantrene - I was actually being tongue-in-cheek with my comment (and name). But alas, there were probably a few head nods from the less informed as they read my statement. It is sad that we have to explain the ridiculousness of "chemical free" to anyone with at least a high school level of education.

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105. Pig Farmer on February 5, 2014 1:30 PM writes...

@#78 Cynical1
You're right. 0.5ppb is rather low as an odor threshold for this chemical, and I think I misunderstood or misremembered what my colleague told me. Here's a link to an article in the WV gazette:
http://www.wvgazette.com/News/201401310118?page=2&build=cache

Louisville water company have been working on this, and they've come up with an odor threshold of 1-3ppb.

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106. Paveway IV on February 9, 2014 6:02 PM writes...

Seriously, Derek... Where do you get your technical information from - CNN?

No coal-washing company on earth could afford to use purified MCHM as a frothing agent. Eastman does not sell pure MCHM to anybody for that purpose - it specifically sells knuckleheads like Freedom 'Crude MCHM', which is the unpurified waste stream from their CHDM resin manufacturing process. It's used as a frother because it's cheap chemical waste, not because it's the best frothing agent.

Didn't the other listed use as a 'fuel additive' tip you off that this is something undesirable Eastman is trying to get rid of?

Crude MCHM *should* contain both water and methanol because they're a byproduct of the reactions to produce DMCD and MCHM. The DMCD is further hydrolysed to produce CHDM resin. CHDM is the glycol that puts the 'G' in PETG plastics.

Regardless of how Eastman markets this stuff, Crude MCHM is produced by the tons at their Kingsport CHDM resin lines. Any industrial chemist should snort at the 'found use' as a coal frothing agent. An accountant or manager 'discovered' that, not a chemist.

I can get the coal industry several hundred thousand tons of equally effective and equally questionably toxic 'frothing agents'. In fact, refiners, chem plants and manufacturers would gladly pay me to haul it away for them.

That would, of course, be the epitome of irresponsible and immoral behavior. Providing any dangerous chemicals to the coal industry is like handing a caveman a nuclear weapon. It would only be a matter of time before bad things happened.

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107. Paveway IV on February 9, 2014 6:17 PM writes...

Reference for the process for all you alicyclic hydrocarbon fans out there:

http://goo.gl/L28mRx

I was going to say 'resin fans', but...

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108. Paveway IV on February 10, 2014 10:55 PM writes...

#78 Cynical1 and
#105 Pig Farmer

No way on earth the odor threshold is in the PPB range. You would be hard-pressed to find many people that could detect the extremely light odor of 4-MCHM much in the single-digit parts-per-MILLION range. I would contend that anyone characterizing it as 'mint-like' is probably actually smelling residual menthol.

Occupational hazard reports say concentrations well above threshold (100's of ppm) have a faintly coconut oil/plastic smell. That's what I would expect and that's similar to many other monomer resins. I've never experienced any resin process smelling like licorice.

In any case, it has never been reported as smelling like licorice by anyone, anywhere (that I've ever been able to find) except for the smells associated with Freedom's crude MCHM. That smell is not directly from the pure 4-MCHM component, period. Something else is giving it that smell, not the 4-MCHM.

That may be good or bad - I would have hoped someone analyzed it by now to positively identify that component. It would be a mistake to make a direct association between that smell and 'safe' levels of MCHM or MCHM esthers/aldehydes or the residual DHCD or CHDM in Freedom's 'crude MCHM'.

Incidentally, it is also a mistake to assume that % of any of the glycols or methanol listed on the crude MCHM MSDS are anything but the roughest of estimates. Crude MCHM contains whatever comes out of the resin reactors or whatever Eastman dumps into the bulk containers of it before shipping it out. They had to put some representative amounts on the MSDS sheet when they submitted it, but the coal-washing biz isn't too particular - as long as it gets frothy.

Seriously, you have no idea what Eastman or Freedom put in their crude MCHM until you have the actual tank product samples tested by an independent lab. I'm sure they've done everything possible to prevent that from happening. Since big coal owns the WVDEP, I would doubt sampling was either done at all or done properly. The WVDEP seems to mysteriously lose a lot of samples on the way to the lab, too. I hope I'm overly cynical and they do cough up a proper analysis, but I won't hold my breath.

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109. Another Chemist on February 11, 2014 11:50 PM writes...

Perhaps "beating" TPA into CHDM results in a byproduct similar enough to Anethole or Anisole to have a licorice-like odor. The lack of aromaticity in MCHM didn't make sense at first, less of an issue now since TPA is in play. Just idle conjecture though.

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110. Paveway IV on February 12, 2014 2:21 PM writes...

The area is noted for an abundance of sassafras trees. Safrole pulled from the water plant's filter beds or activated carbon cap were also suggested, but that wouldn't explain the licorice odor reported over the past years from Freedom's crude MCHM handling in the tank farm.

Not sure how close safrole's smell is to licorice - I thought it was more spicy, but my nose has trouble with those. The odor threshold for anise is closer to the single- or double-digit ppb-range, so that would make much more sense.

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111. Paveway IV on February 13, 2014 3:17 AM writes...

More froth porn for chemists: http://goo.gl/YrBvuV

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112. Meghan I. Rosie on September 20, 2014 5:50 PM writes...

Right now it appears like Expression Engine is the preferred
blogging platform out there right now. (from what I've read) Is that what you are using on your blog?

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