Continuing the saga of 4 MCHM spill in Charleston, WV, now some irresponsible so called scientist is making formaldehyde the bogeyman.
This news item linked below is forwarded by one of our great commenters and a chemist, expert on compliance and spills. Mr. Big Boy, BG.
The claim is they found formaldehyde in some water samples from plaintiff restaurants.
Methanol, which is a single carbon with an OH radical on the side, is converted in the body to formaldehyde (HO on the side) by alcohol dehydrogenase and then formaldehyde converts to Formic acid (methanoic acid, COOH) which is the bad boy for living things.
Formic Acid damages kidneys, solid organs, causes blindness. In small amounts formaldehyde is present in living things, a metabolic byproduct.
Alcohol Dehydrogense, a human enzyme, breaks down alcohols, like methanol, and Ethyl Alkeehal (the good stuff).
Here is a description of alcohol dehydrogenase, essential to our ability to handle alkeehal.
Structure of alcohol dehydrogenase is discussed here below, just to make sure you die hard evolutionists understand the stupidity of the theory of random shuffling to produce functional complexity.
Alcohol dehydrogenase is a homodimer. Each monomer has 374 residues with molecular weight of 74000 dalton. ( A Dalton is 1/12 of a Carbon nucleus, so 74000 means a little more than 6 thousand carbons in various molecules) There are two domains. The NAD+-binding domain (residues 176-318) consists of a central beta-sheet of 6 strands flanked by alpha helices. NAD+ binds to the C-terminus of the beta-sheet. The catalytic domain (residues 1-175, 319-374) also has a alpha/beta structure. The inter-domain interface forms a cleft which contains the active catalytic site. The interface is formed by two helices, one from each domain crossing over each other. There are two Zn++ cations per monomer, one at the catalytic site being mandatory for catalysis. The alcohol substrate binds inside the cleft where the Zn++ cation is, whilst the nicotinamide ring of the NAD finds its way pointing into the cleft. The dimer forms with the two NAD-binding domains packing together such that their 2 central beta sheets combine to form a 12-stranded beta sheet. The catalytic domains are situated at opposite ends.
4MCHM, the agent in the spill is a big molecule (Dalton size 96) with a methyl hanging off one side of the ring and a methanol hanging off the other side.
Alcohol Dehydrogenase (AD) is specifically designed (woops, maybe just accidentally happens) to work on alcohols and turn them into aldehydes and ketones.
AD doesn’t have the ability to knock off the methanol from the Cyclohexane ring so that somehow a formaldehyde to formic acid thing could happen. However, even though I am not an organic chemist, I am not stupid and there is a Holiday Inn Express here in my home town, so I will propose the following at least for consideration, and criticism.
If I leave 4MCHM in a solution some methanol will spontaneously form. If i heat it up, more will form. Also formaldehyde. I would have to really heat it up to make methanol or formaldehyde. Since formaldehyde is a simple molecule simple reactions might result in breakdown to formaldehyde from solutions with organic chemicals in them.
AAAAANNNNDDD we suffer from extremely sensitive instruments. There is formaldehyde in our bodies, why should we be surprised to find it in a random water sample if we set the sensitivity high enough?
That’s why, for all us Holiday Inn Express scientists we remind the ignorant anxious lay people and media–dose makes the poison, not how scary the name of the chemical sounds.
http://www.usatoday.com/story/news/nation/2014/01/29/freedom-industries-spill-formaldehyde/5031963/
You can count on USA Today to get it wrong though, and to perpetuate panic when possible–sells newspapers and promotes gov action and agency status as saving us from those evil capitalists.
Who says chemicals are not a good thing? They are the life blood of trial lawyers.
MN Mass Spec guy: You sound like an analytical chemist. I am an organic chemist and I see no way that chlorine could attack methyl cyclohexanemethanol and produce formaldehyde or methanol. In my opinion that is hogwash. There is no way that MCHM could decompose to methanol in even boiling water. Chemophobia runs rampant in this country aided and abeted by opinions such as yours.
I’d welcome an reaction pathway that takes any of the constituents of crude MCHM to formaldehyde in dilute aqueous solutions, even in the presence of some disinfection. I admit that I didn’t look at the disinfection method used by American Water, but Cl2 or chloramine are likely constituents. I couldn’t come up with one. I never said I wasn’t an Organic Chemist. I have a couple degrees that say “Organic Chemistry.” and a post-doc in stereochemistry. My industrial experience includes formaldehyde-amine condensation products and about 10 Michigan waste water operator certifications. That makes me an organic turd herder.
As for “small concentrations” I’m hard pressed to come up with a way to come up with 750-2000 ppm concentration in air from an aqueous solution containing up to 0.03 ppm CH2O, even if you consider the atmospheric dilution is the breathing zone of the person taking the shower. Remember, you’d have to have much higher since showers may not take as much as 15 minutes.
BTW: I’ve been impressed with modern mass spec. Back in the days just after phlogiston, my mass spec pubs consisted of elucidating fragmentation pathways. The stuff they are doing now makes me feel like a cave man.
Yes, potent toxins. That’s why every city with Chlorinated water has experienced a reduction in mean life expectancy dating back to the start date of chlorination, right? Then there’s also the isolated areas with historically bad health due to naturally chlorinated water. I’m sure you’ve “cranked the numbers” on that. Certainly you aren’t simply regurgitating hypotheticals without studying real world application.
Nice flame – Data? facts? chemistry?
My goodness, are you a little leftist troller? You know so little and speak so much.
However, might I again remind you that dose makes the poison. Don’t tell me how pharmaceuticals work. You only know how to sneer, and you certainly don’t know anything about pharmaceuticals.
Glad you admit you’re not an Organic Chemist. Otherwise, you’d know that chlorination of drinking water always results in disinfection by-product molecules. Many of these are potent toxins. Chemical attack by chlorine on MCHM could directly result in formaldehyde.
If you doubt that “small concentrations” matter – you’ve never cranked the numbers on how pharmaceuticals work – often at ppb levels!
Yes, ppb, so your 8hr exposure limit is 750 ppb. Very likely the results are stomping all over their detection or quantitation limits.
“The formaldehyde measurements were some samples showing ~30 ppb.” Just checking here, that’s parts per BILLION, right? Some times I think the world would be better off if our measuring equipment was less sensitive.
Could the Formaldehyde be present as a result of wood burning fireplaces/stoves?
The metabolic pathway for methanol works to make formaldehyde, but I’m hard pressed to see how that happens in water. If 4-methylcyclohexylmethanol could break down in a very short time to some reasonable amount of methanol it wouldn’t be much use as a frother. Someone suggested that the polygycol ethers in the MCHM might do that. I can’t come up with a reasonable chemical mechanism. Formaldehyde makes methanol and formic acid via the Cannizaro Reaction. The state says if you combust (burn) it at 500°F you can create some formaldehyde. That’s pretty much true for most hydrocarbon combustion processes. It is unlikely that taking a hot shower will do that.
The formaldehyde measurements were some samples showing ~30 ppb. The OSHA TWA (8 hour) is 0.75 ppm (air) and the PEL (15 min) is 2 ppm. Formaldehyde vapors irritate eyes, nose, throat and lungs. You start noticing it at ~0.1-0.2 ppm and won’t stay long in an area that is 0.5 ppm. So how does short exposure to whatever vapor concentration you get from 30 ppb in water for the time required to take a shower make this a big, scary problem other than feeding someone’s agenda?