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Medicine

Novel Fluorinated Compounds Discovered In Firefighters' Blood 87

ckwu writes: Perfluorinated compounds help firefighting foams rapidly flow over flaming liquids such as gasoline and jet fuel, cooling and quenching fires. But despite environmental scientists' concerns about these possibly toxic compounds, researchers don't know the identity of many of the chemicals in the mixtures on the market. For the first time, a new study borrows a medical research tool to pinpoint fluorochemicals in the blood of firefighters, identifying novel compounds that have never before been publicly reported.
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Novel Fluorinated Compounds Discovered In Firefighters' Blood

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  • by Harlequin80 ( 1671040 ) on Tuesday February 03, 2015 @09:29PM (#48975449)

    I would have thought that something used by the fireservice in large quantities and knowingly dispersed into the wider environment would have its chemical composition well known.

    There are a multitude of environmental, health and liability issues here and I simply don't buy it that the ingredients are a mystery. I'm sure that there are chemicals available which are excellent at fire fighting but also highly toxic and that those chemicals aren't used because of their lethality.

    I can just imaging the defence now. "So Mr Government, you're telling me that you gave firefighters this product, to use on fires in public spaces where both trained personnel and the public can be expected to be and you didn't know what was in it?" "Correct" "Prosecution rests its case"

    • by TWX ( 665546 )
      This is a guess, but since usually the consequence of not using one's options to put out the fires are to have fires the burn out of control, I'm not really surprised that these things aren't well tested. In emergencies a lot of things are overlooked.

      If there are consequences to exposure, then this needs to be addressed before it kills the very people that are trying to save us.
      • by Anonymous Coward

        In emergencies a lot of things are overlooked.

        In emergencies fire fighters don't just pick up random shit lying around the place, throw it on the fire, and say, "well, did that make it better or worse?" There are many tests conducted ahead of time before different things are added to the standard equipment. The problem here is that some of those tests seemed to have missed the lethality of the compounds used in various surfactants.

        • Re: (Score:2, Insightful)

          by Anonymous Coward

          Do you have any evidence of the lethality of them? I've got pretty good evidence that firefighters are living with them in the blood, and, well, no evidence, at all, to suggest that these are causal for any cancers. Fire is nasty. Fires create all sorts of imaginable and many unimaginable carcinogens (large sooty molecules). Pointing to a particular class of florinated compounds, and then asserting that they're only from foam, which is used only on liquid fuel fires, is a bit of a stretch. If you want to se

        • by gl4ss ( 559668 )

          it's probably less lethal than inhaling fumes from burning rubber and jet fuel....

          so.. it's better than what they had before.

      • In emergencies a lot of things are overlooked.

        The needs of the many outweigh the needs of the few. Or the one.

    • I also cannot believe that the companies producing these compounds do not know what is in them, or that the government would allow them to be employed or transported with no knowledge of what they contained. I would, however, expect that once they are applied to any number of materials in a high-temperature environment with ongoing combustion that all bets are off, is it possible this is what they are looking for?
      • by Will.Woodhull ( 1038600 ) <wwoodhull@gmail.com> on Tuesday February 03, 2015 @10:43PM (#48975843) Homepage Journal

        Is this the Dumb and Dumber show? Is slashdot in a mad race toward the lowest IQ that can still author a comment? Come on, guys, you are giving nerds and geeks a bad name.

        You do realize it would take a thick book to document all the chemical changes that happen in a candle flame? (Everyone here has seen a candle flame at least once, right?) And that candle flame is a highly controlled burn.

        So do you really think anyone can add a known fluorinated chemistry to a wild fire that is creating all kinds of products of incomplete combustion and have any idea how one of the most reactive elements in the periodic table is going to combine with who the hell knows what?

        Of course no one knows what the chemical compositions of the stuff that is getting into the firefighters might be. All they can recover is the products after a second very complex set of chemical reactions; after whatever further reactions occur in the lungs or the blood or maybe the liver. At this point, even the portal of entry can only be guessed at. The environmental chemists have their work cut out for them on this one.

        • But this isn't the premise of the summary. It may be the premise of the article but hey this is slashdot!

          From the summary "researchers don't know the identity of many of the chemicals in the mixtures on the market."

          I think trying to argue that we don't know what firefighters inhale when they are fighting fires is a bit of a given, cause we don't know the contents of what is burning. Or at least to me it is and perhaps that sticks me in the dumb and dumber camp.

          So now I have had to go and read the article

        • by Bob_Who ( 926234 )

          Yes, indeed. Fluorinated chemistry is potentially lethal - Fluorine is the most reactive of all elements and has martyred many chemists.

          • by fonske ( 1224340 )
            And once Fluorine has reacted with carbon it is incredible stable.
            BUT:
            it has superacid properties and as such is used as catalyst.
            Toxicity is well established especially of the small molecule PFOS.
            Since it is stable you can already guess the environmental problem?

            I once identified Nafion (branched oxygenated form) on a TOF-SIMS and had this crazy phone from my client:
            - Whassup with this Mafion ("queer" ion in Dutch) you detected?
            - Sir, you certainly mean Nafion?
            The guy kept calling it queer ion thr
      • by Harlequin80 ( 1671040 ) on Tuesday February 03, 2015 @11:26PM (#48976151)

        Not according to the article. It is a scare pamphlet about how 3m had a compound in foam that they removed in 2002 due to toxicity concerns and that the replacement must also be toxic because it doesn't have a specific name.

        Side effects of combustion are NEVER touched upon

    • . I'm sure that there are chemicals available which are excellent at fire fighting but also highly toxic and that those chemicals aren't used because of their lethality.

      Since my town has started using Agent Orange to fight fires . . . we have drastically reduced the costs of the firefighters' pension fund.

      Fighting fires is a real shitty job . . . you get exposed to all sorts of nasty toxic fumes . . . and you might even have flaming rafters collapse on you.

      When I was a kid, being a fireman was one of those "what do you want to be when you grow up?" careers. But now, I really can't understand why those folks do it. I guess it might have something to do with conquering n

    • by Anonymous Coward

      Reminds me of oil dispersants.

    • I would have thought that something used by the fireservice in large quantities and knowingly dispersed into the wider environment would have its chemical composition well known.

      Well yes, that would make sense, in a perfect world. But in ours, if a patented or otherwise proprietary product helps you stay alive, you use it. You use it even if you don't know how dangerous it is in its own right, since you know for a fact that fire is dangerous.

      I know a couple of fierfighters, and I guarantee they've never asked what is in their suppressants, because they have simply learned through experience to trust them. Of course this is less than ideal (to put id mildly), but it should not be

      • I wouldn't expect the firefighters themselves to know. In much the same way I wouldn't expect them to know the specifications of the valve liner in the engine of their truck, or the impeller angle in their water pump.

        However I would absolutely expect the organisation to know. To have had someone do a risk assessment on the materials used by the front line operators. The health a safety department should know what chemicals they are going to be exposed to from their own equipment. To not know this is neg

    • I can just imaging the defence now. "So Mr Government, you're telling me that you gave firefighters this product, to use on fires in public spaces where both trained personnel and the public can be expected to be and you didn't know what was in it?" "Correct" "Prosecution rests its case"

      No one cares what's in it. No one knows what's in most things. What's important is what it does and how to treat it.

      You don't know the chemical composition of many items you use on a daily basis but know how to handle them very well. A Material Safety Data Sheet comes with all these products and will give you information on the Material. It will NOT give you a complete list of compounds or a chemical formula.

    • by Tailhook ( 98486 ) on Wednesday February 04, 2015 @01:04AM (#48976753)

      I would have thought

      You have inflated expectations of our knowledge.

      Buckyballs are common in nature. They proliferate around campfires. We didn't realize that until after we "first generated" (as Wikipedia puts it) buckyballs in a lab and awarded Nobel Prizes for it thirty years ago.

      When some chemical company reacts Fluorine with whatever to make fire retardant is it really surprising that a variety of molecular species appear? We don't actually put each molecule under a STEM and serialize it. The product is "mostly" some intended molecule and the rest is..... meh. Whatever!

      You live in that world. You are wearing it, eating it and using a big pile of polymer and highly refined minerals to demonstrate your ignorance with it, and despite the fact that we probably haven't cataloged more than a fraction of what all that stuff is out-gassing into your lungs you'll probably live to be a ripe old 90+ because of it. So try not to spaz out about it.

      These Fluorine compounds are close to inert which is why they persist so long. Unless the firefighters are actually eating their fire retardant with coffee each morning they are unlikely to suffer any effects at all from the minuscule amounts that manage to get past their filters and whatnot. And if they do then they have their gold plated government funded health care, public union negotiated disability plans and similarly generous pensions to help them cope. Fighting fires is a dangerous occupation.

      • When some chemical company reacts Fluorine with whatever to make fire retardant is it really surprising that a variety of molecular species appear?

        Also, what happens when you spray the stuff on a burning house? These fluorine compounds are probably the least of firefighters' worries because of how homes are made. They're made out of galvanized metal (zinc is horrible) and by code they must have wiring sheathed in PVC (releases dioxin when it burns) and they're typically made out of a whole lot of chipboard (dioxin) and plywood (dioxin) and that's before we even get to all the coatings, paints, varnishes, blah blah blah.

        Of course, we all get to breathe

        • by cdrudge ( 68377 )

          why are we even building flammable houses?

          I don't know, maybe to save a human life?

          • why are we even building flammable houses?

            I don't know, maybe to save a human life?

            Which of the words in my comment was unclear to you?

        • Meanwhile, why are we even building flammable houses?

          Because we don't want to live in caves? Because concrete is too cold in the winter unless you add tons of flammable materials to keep one warm?

          In the interest of openmindedness, kindly elaborate on what you think we should be making houses with such that they don't burn.
          • Because we don't want to live in caves? Because concrete is too cold in the winter unless you add tons of flammable materials to keep one warm?

            Did you know these were stupid things to say when you said them, or are you just finding out now?

            In any case, http://www.earthbagbuilding.co... [earthbagbuilding.com]

            To say nothing of stuff like steel roofing and siding. It should seriously be illegal to build a wooden roof in fire country.

      • by AK Marc ( 707885 )

        that manage to get past their filters and whatnot.

        Around here at least, the firemen use no filters of any kind at any time. They are either far enough away to not need anything, or breathing tank air. I guess a fireman could carry some personal dust masks they throw on when they feel like it, but I'd imagine that would get them teased.

      • " And if they do then they have their gold plated government funded health care, public union negotiated disability plans and similarly generous pensions to help them cope."

        Tell that to the 800,000 firefighters in the USA who are unpaid, non-union, volunteer firefighters.

        • by Tailhook ( 98486 )
          Of course, the operative word there is "volunteer." If trace amounts of inert Fluorine compounds are a serious concern for someone, in addition to the asbestos, dioxin, carbon monoxide, benzene, sulphur dioxide, hydrogen cyanide, aldehydes, lead, hydrogen chloride, zinc, silicates, dichlorofluoromethane and only god knows what else that any given volunteer is likely to encounter, then the thing to do is not volunteer. I suspect the net number of volunteer's that abandon their role as firefighters due to F
    • by qeveren ( 318805 )

      ... and then they get a pittance of a fine and go about continuing to do business.

    • Dude, seriously, we don't know what's in fracking solutions.

      "Proprietary formulation" and "trade secrets" are used all the frickin' time for companies to claim that they can't tell you what they're using because they say it's a secret and how they make money.

      The companies making this stuff know exactly what they put in it. Make no mistake about it.

      But if you think this is the only example of companies not disclosing that kind of stuff, you simply haven't been paying attention.

      And governments seem quite wi

      • I find that crazy strange. As in it is totally different here in Queensland where there is also lots of fracking happening.

        http://www.ehp.qld.gov.au/mana... [qld.gov.au]

        How does the government monitor fraccing activities?
        Prior to undertaking fraccing activities operators must:
        provide details of their proposed fraccing operations, including the location of wells;
        detail the chemicals to be used and the toxicity of ingredients and mixtures; and
        develop a stimulation management plan that must be co

    • It is called intellectual property. Once a company claims that there product is protected they do not have to disclose whats in it. Look at fracking mixtures. We take the trust us it is safe to people instead of give us a list of whats in it.
      The same issue is shown here. Company makes product and yes it puts out fires really well. That is all they test for.
      We need laws that state you must list and test what is in your product to make sure it is safe in how it is being applied.

      • But the liability for giving something toxic to the firefighters would sit with the overall fire fighting department and then their masters the local government. An argument that "it's covered by intellectual property so we couldn't determine if it was safe" will be met with a "don't use it then response".

        Onus rests on the fire department to ensure that they are not using toxic materials without knowledge or training.

  • deathtrap (Score:4, Insightful)

    by Virtucon ( 127420 ) on Tuesday February 03, 2015 @09:31PM (#48975455)

    so in an attempt to save property we're subjecting firefighters to increased risk of cancer and thyroid disease.

    • by Anonymous Coward on Tuesday February 03, 2015 @09:38PM (#48975491)

      ...this was found in their blood, implying that the firefighters are just evolving a natural defense against fire.

    • It's property and lives, and, yes, facing risks on our behalf is pretty much what we ask firefighters to do every single day.

      That's not to say, of course, that we should make them guinea pigs for inadequately tested compounds, or stooges for suppliers trying to cut corners on cost and safety.

      • That's pretty much it.

        Firefighters know that being a firefighter is risky. There are the obvious dangers during the emergency, and some less obvious ones like lung damage, extended fatigue, traumatic horror... ...and now a bit of chemical risk as well. To someone who expects to risk their lives for the sake of others, this is just another item in the long list of hazards.

        Sure, we should do our best to investigate the hazards and minimize them, but overall I think this might just be one of the least-dangerou

    • Firefighters here are canaries. It's not like these chemicals are recycled nor used sparingly. Down the drain it goes; where they bio-accumulate, yeah, what ever. Minimum waged disaster restore specialists doing mop-up are in the thick of it too.
    • so in an attempt to save property we're subjecting firefighters to increased risk of cancer and thyroid disease.

      This is not news to any firefighter. A lot of them get cancer, but this has nothing to do with the foam and a lot to do with the fact they work around thermally decomposing chemicals.

      It's not the foam that will kill, it's inhaling the fumes from a house fire on a daily basis.

      • The foam is used to end the fires. The smoke from the fires is highly carciogenic (most smoke is).
        Ergo, if the fluor compound is only lightly carciogenic (and biodegradable) there is a net win.

  • What, no MSDS? (Score:4, Interesting)

    by __aaltlg1547 ( 2541114 ) on Tuesday February 03, 2015 @10:08PM (#48975655)

    "researchers don't know the identity of many of the chemicals in the mixtures on the market."

    Doesn't pass the smell test.

    • Re:What, no MSDS? (Score:5, Interesting)

      by reverseengineer ( 580922 ) on Wednesday February 04, 2015 @12:08AM (#48976427)

      I don't know- I went looking for an MSDS for a modern firefighting foam, and the composition listed [tyco.com] is:

      Polyethylene glycol: 2.5-10%
      Other components below reportable levels: Greater than 90%

      Now, this is for Ansul-3 Fluoroprotein foam concentrate. It definitely contains some sort of fluorinated compound (fluoroprotein foam agents are at least known to contain a fluorinated surfactant and hydrolyzed protein); the MSDS has absolutely no mention of what it is. In the Environmental Handling section, all it says is "An environmental hazard cannot be excluded in the event of unprofessional handling or disposal." Nothing about how fluorinated surfactants are persistent environmental contaminants or can cause kidney damage in high doses. It is simply written like innocuous polyethylene glycol is the only component. I've seen material safety data sheets for shampoo that have far more information.

      Now, in the specific case covered by the research paper, the "unknown compounds" aren't really that mysterious. They're all either metabolites, chemical precursors, or close chemical relatives (if you're making some some sort of octane derivative, you can expect some hexane to be in there too). And they're all given as 0.1%-1% of the main PFOS surfactant; certainly chemical manufacturers need to exert better control over their processes, minimize byproducts, perform long-term safety studies, etc. And that goes double for anyone making halogenated organic compounds, which now have a substantial record of turning out to be accumulative toxins. But I think if you look at many common manufactured products at trace levels with tandem mass spec, you're going to find some compounds that aren't in the literature.

    • MSDS does NOT give a full chemical composition of a liquid. Many of these are trade secrets and the only the reportables are reported.

      Yes most of this stuff is nasty for the environment and a lot of it is carcinogenic too. That information is reported.

  • by Anonymous Coward

    On the plus side there's not been one firefighter death due to spontaneous combustion. Also.. in a pinch the blood of your colleagues can be used to put out gasoline fires.

  • by ihtoit ( 3393327 ) on Tuesday February 03, 2015 @10:10PM (#48975671)

    Don't firefighters have the right to know about the compounds they're using, for example what to do in case of inhalation of certain gases (halons come to mind) or skin contact with certain foams (eg the ones that contain fluorocarbons, that absorb through the SKIN)!?

    IANAFF (I am not a firefighter) but if I were I would be REFUSING to use anything that I didn't know about that has the potential to react badly with any part of my anatomy, and that includes fire retardent FC foams, smothering heavy gases, bubble blankets... job be damned, my job is to fight fires not knowingly endanger myself in ignorance of potential AND AVOIDABLE hazards.

    • Based on having gone through the firefighter training courses numerous times for my job, talking with the guy who wrote the textbook on firefighting, and generally being around a firefighting school, this article sounds bunk to me. Heck, even the non-firefighter classes for IT security people cover the important risks of halon and some other firefighting materials.

      It's claimed that "they" don't know what's in the foam. May be "they", the people who wrote the article, don't know, but I'm pretty sure our i

      • Knowing what is in something and knowing what it does are not the same thing. The toxicity and environmental impact of the substances are known and reported. The exact chemical composition is actually very irrelevant.

        Also firefighters don't have much to fear from foam. Most of them would die from cancer caused by inhaling decomposition components of dangerous chemicals anyway. There's a reason firefighters can no barely go near a fire without donning a self contained breathing apparatus. I'm not talking abo

      • It's claimed that "they" don't know what's in the foam. May be "they", the people who wrote the article, don't know, but I'm pretty sure our instructors know exactly what it is.

        What. Fucking. Year. Is. It. Go check the MSDS for yourself, and you can see precisely what your instructors know about these compounds. Anything else they think they know is probably wrong.

        I was talking to one of the instructors about trying to come up with a "poor man's" sprinkler system you could put it the kitchen or other high-risk areas and it sounds to me like he knows what the different systems use.

        So because it sounded like he knew what he was talking about, you believe he knew what he was talking about? That's ignorant at best.

      • by AK Marc ( 707885 )
        What we use is a mix of soap and anti-freeze. The soap helps the water penetrate surfaces, and the anti-freeze helps raise the boiling point of water, to increase the amount of heat it can extract from the fire. The foam used by airport fire teams is different, and I don't know what's in it. In general, if you are on a hydrant, and don't have flammable liquids, you'll never use the foam anyway.
        • So you're a firefighter? If you ever come out to TEEX for training I'd like to buy you lunch.

          • by AK Marc ( 707885 )
            I hung out at TEEX all the time, when I went to A&M. But that was back in the '90s. I've moved out of the US now, and haven't been to Texas in many years. And when I hung out there, it was mainly for the TTI or other transportation-related things over at Riverside. The cool fire-fighting stuff was at Easterwood, where they'd make huge plumes of smoke every few months.
  • Firefoam Man?

    Perfluoro Carlton?

    Teflon Ted?

    In all serious, finding novel compounds is interesting and important, but not in your own blood.

  • by Anonymous Coward

    The story here isn't some novel way to find chemical compounds in a substance by testing humans. That's cool, but the real story here is why the hell don't we know?

    We know our politicians in the US are able to be purchased by a high bidder, but are the companies providing firefighting compounds part of the bidders? This is the system that has given us unknown fracking compounds, manufactured doubt about climate change, and attempted coverups for oil and chemical spills. We should ask China how well that'

    • This is the system that has given us unknown fracking compounds, manufactured doubt about climate change,

      should be

      This is the system that has given us manufactured doubt about fracking compounds, unknown [effects of] climate change,

      Trying to act like unknown fracking compounds matters in any way is fud at best. Fracking compounds are pumped so deep, and used on geology that has contained a volatile gas for millions of years, and you are concerned about what they pump down there? There is NO WAY for the fracking fluid to get into water, if there was, the gas would have long ago been in the water table. All of the studies done have shown that either the "zomg flammable water" was there before any fracking happened.

  • by redelm ( 54142 ) on Tuesday February 03, 2015 @11:23PM (#48976099) Homepage

    We hardly know everything that is in gasoline (about a hundred compounds, mostly C4-C9 isomers). Jet fuel is more complex and diesel (C10-C20) is just too far gone.

    Why would you expect to know the exact isomers (and recemization) in a fluorinated organic? The fluorine will go on in various places. And even if you think you know, it will change once thermally cracked at fire temperatures.

    Mostly harmless, but there will be the odd one with just the wrong geometry to do somethink nasty, like the way BPA binds estrogen receptors.

  • Novel compounds found in writers' blood.

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