Ooops – According to NASA, ozone destroying CCl4 remains in atmosphere, and continues to be emitted

Carbon-tetrachloride-3D-balls

Carbon-tetrachloride

NASA research shows Earth’s atmosphere contains an unexpectedly large amount of an ozone-depleting compound from an unknown source decades after the compound was banned worldwide.

Carbon tetrachloride (CCl4), which was once used in applications such as dry cleaning and as a fire-extinguishing agent, was regulated in 1987 under the Montreal Protocol along with other chlorofluorocarbons that destroy ozone and contribute to the ozone hole over Antarctica. Parties to the Montreal Protocol reported zero new CCl4 emissions between 2007-2012.

However, the new research shows worldwide emissions of CCl4 average 39 kilotons per year, approximately 30 percent of peak emissions prior to the international treaty going into effect.

“We are not supposed to be seeing this at all,” said Qing Liang, an atmospheric scientist at NASA’s Goddard Space Flight Center in Greenbelt, Maryland, and lead author of the study. “It is now apparent there are either unidentified industrial leakages, large emissions from contaminated sites, or unknown CCl4 sources.”

NASA video discusses new research that shows Earth’s atmosphere contains an unexpectedly large amount of an ozone-depleting compound from an unknown source decades after the compound was banned worldwide.

As of 2008, CCl4 accounted for about 11 percent of chlorine available for ozone depletion, which is not enough to alter the decreasing trend of ozone-depleting substances. Still, scientists and regulators want to know the source of the unexplained emissions.

For almost a decade, scientists have debated why the observed levels of CCl4 in the atmosphere have declined slower than expectations, which are based on what is known about how the compound is destroyed by solar radiation and other natural processes.

“Is there a physical CCl4 loss process we don’t understand, or are there emission sources that go unreported or are not identified?” Liang said.

With zero CCl4 emissions reported between 2007-2012, atmospheric concentrations of the compound should have declined at an expected rate of 4 percent per year. Observations from the ground showed atmospheric concentrations were only declining by 1 percent per year.

To investigate the discrepancy, Liang and colleagues used NASA’s 3-D GEOS Chemistry Climate Model and data from global networks of ground-based observations. The CCl4 measurements used in the study were made by scientists at the National Oceanic and Atmospheric Administration’s (NOAA’s) Earth System Research Laboratory and NOAA’s Cooperative Institute for Research in Environmental Sciences at the University of Colorado, Boulder.

Model simulations of global atmospheric chemistry and the losses of CCl4 due to interactions with soil and the oceans pointed to an unidentified ongoing current source of CCl4. The results produced the first quantitative estimate of average global CCl4 emissions from 2000-2012.

In addition to unexplained sources of CCl4, the model results showed the chemical stays in the atmosphere 40 percent longer than previously thought. The research was published online in the Aug. 18 issue of Geophysical Research Letters.

“People believe the emissions of ozone-depleting substances have stopped because of the Montreal Protocol,” said Paul Newman, chief scientist for atmospheres at NASA’s Goddard Space Flight Center, and a co-author of the study. “Unfortunately, there is still a major source of CCl4 out in the world.”

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75 thoughts on “Ooops – According to NASA, ozone destroying CCl4 remains in atmosphere, and continues to be emitted

  1. “In addition to unexplained sources of CCl4, the model results showed the chemical stays in the atmosphere 40 percent longer than previously thought.”

    I think it’s clear that between “unexplained sources” and “stays in the atmosphere 40 percent longer,” they have no clue what’s going on. Is the carbon tet in the atmosphere from new sources or longer retention? They don’t know. So claiming there are new sources is just speculation.

  2. Gee – not only are they confounded by “unintended consequences”, but now we see they’re confounded by unexpected everything.

    Funny thing about assuming everything “harmful” being “human caused”… you’ll always be shocked when you find it’s not.

  3. They were banned from sale and production, not from possession. Thousands of fire extinguishers are still around full of carbon tet. Easiest way to dispose of is squirt on the ground or throw the glass container at a rock. Or put in the garbage so the chemical will be slow released from the land fill. Not much of a surprise.

  4. Lots of that used in the production of polycrystalline silicon for cheap Chinese solar cells. But we can ignore that. Everyone knows solar is ever so clean and green….

  5. Here’s the funny thing: the ozone hole is closing way faster than predicted when they passed all of those “ozone depleting chemical” bans. There’s a lot more Freon and CCl4 in the atmosphere than there should be (some countries are still making Freon and similar products).

    So why is the ozone hole not getting bigger? We were told – with little reservation – that even if we passed the Montreal Protocol, it would take until about 2050 for the ozone hole to stabilize and start to shrink, because it would take that long for those chemicals to break down.

  6. I’m going with the marine algae hypothesis.

    So we need to look at ice core bubbles? Perhaps there has always been carbon tet being produced. Which of course means that humans were never the only significant source to begin with, which means that the atmosphere was stable with 40% prior production maximum ….

    Somewhat like CO2? There is a non-human source, recent or not, which is not being considered in the balance, which means that we can’t stop the CO2 rise right now by killing the industrial economy …….?

  7. In just the last 5 years I have taken one 1950s chest freezer and two 1970s airconditioners to the scrap yard, after I took the copper out of them of course, also I know where 6 cars built in the 70s are stored with working air conditioning and slated for restoration, no reclamation was or will be done.

    And I am just one person, probably a lot more of this going on than people realise

  8. adam says:
    August 20, 2014 at 4:02 pm

    No one would ever cheat.

    I wonder if a satellite could trace the sources, the way the new satellite is going to trace sources of CO2.

  9. Carbon tetrachloride still has some industrial and research uses. You can buy it from Aldrich and Fisher. So, “banned” is a rather loose term. “Unexpectedly high” seems to imply a natural source.

  10. Let’s see… China still makes it, and has authorized it’s industries to use some 32,000 Tonnes of the stuff. Gee, I wonder if anybody is fudging the numbers there?

  11. DaveK says:
    August 20, 2014 at 4:50 pm
    Let’s see… China still makes it, and has authorized it’s industries to use some 32,000 Tonnes of the stuff. Gee, I wonder if anybody is fudging the numbers there?

    Maybe NASA already knows that, and wants to send a message, but diplomatically didn’t point a finger.

  12. Haow many Gigatons of extra carbon were put in the atmosphere to comply with obviously not working Montreal protocol? Can I get energy efficient air conditioning back now or or do I still have to use the massive carbon footprint of replacement chemical compressors?

    P.S. the Shuttle astronauts that died because the foam process had to change for CFC compliance want their lives back.

  13. Saw a report a coule of years back where the US (and probably others) military was using it as a degreaser for equipment wash down before maintenance work. Basically pressure washing with the stuff outdoors.

  14. 108 Countries Support HFC Curbs under Montreal Protocol – Posted November 24, 2011
    The good news: Support continued to grow in Bali for taking steps to avoid disastrous increases in production of HFCs. 108 countries – more than half the world’s nations – have now backed moving forward on HFC phase-down proposals from Micronesia and from Canada, Mexico, and the United States. That’s up from 91 supporters last year and 41 two years ago. (The countries are listed below.)

    The bad news: India, China, and Brazil still stand in the way.

    http://switchboard.nrdc.org/blogs/ddoniger/1xx_countries_support_hfc_curb.html

    39 kilotons per year in an atomosphere of 5. x 10^13 Ktons equals what percent?

  15. Dave says:
    August 20, 2014 at 5:44 pm

    It was used as a cleaning agent in parts washers and also applied by brush, in the Australian Military.

  16. “People believe the emissions of ozone-depleting substances have stopped because of the Montreal Protocol,”
    ============
    Define “people”.

  17. Okay, contaminated sites – yes, Landfills – yes, old stashes still being use – probably.

    When I looked at a substance supposedly banned by Europe back in the 90s at the behest of the UK DoE, I could account for the UK’s contribution, but we were the only ones to report, everybody else claimed it was too difficult and therefore unknown.

    My guess would be that everybody’s fudging the numbers!

  18. Kids used to buy little cans of carbon tet to use for their science class bug collection project. It was usually found on store shelves near the laundry supplies. A few drops on a cotton ball n a jar… drop in the bug and close the lid… yielding an intact insect that could be mounted with one of those long thin steel pins that the teacher had ordered from the Gilbert Scientific catalog.

  19. I’d blame third world dry cleaners.

    The graphics I’ve seen don’t show much more than natural variation in the Antarctic ozone hole after the Montreal protocol passed. The interesting thing is that there is ozone in concentrated arcs surrounding the hole, much as though the ozone in the middle has not been destroyed, merely swept outward from the pole.

  20. So this will be the next thing to fear? After they let CO2 off the hook, that is (okay, okay, too much to hope for – after they let it slide, then, how’s that?). Looks like it’s going to be out with the old, in with the new – Human caused, catastrophic and something to do with industry and thus civilization, of course.

    I don’t know if we’re going to end up with an uprising to finally get these monkeys off our backs, but something’s got to give. Not being able to fool all of the people all of the time will have something to do with it.

  21. Sounds like the substance could be cming from many sources – why do they believe that just because it was banned , it would magically disappear? Sounds like they were being awfully gullible and thought, well, job done. What’s next? I wonder if they even had a cue as to how much of the stuff was still contained in a variety of objects.

  22. And the prize for the most stupid comment goes to…

    “markx says:

    August 20, 2014 at 6:00 pm

    You’d reckon they could have made an exception for asthma inhalers:

    http://www.kevinmd.com/blog/2009/03/why-does-my-new-asthma-inhaler-suck.html

    the new inhalers, which use hydrofluoroalkane (HFA) as a propellant, have been attracting a litany of patient complaints, including that the medicine tastes funny, the propellant isn’t as strong, it’s less effective, and it costs much more.”

  23. There you go.
    The science is settled.
    Of course they have no idea, this Ozone hole scare was a test run that lead to the CAGW, CO2 as a magic gas scheme.
    It would not surprise me in the least to learn there is a natural source for carbon tetrachloride, as the only thing certain about climate sciences is their smug certainty.

  24. CCl4 is still made by China, India and others. No surprise that they are finding the stuff in the air.
    Before the Montreal protocol took effect production peaked at 960 kilo tons. Not easy to find close to exact numbers now. Plenty of uses for it.
    But to say that there must be a source somewhere while there should not be. Common.
    Who are you kidding.

  25. philjourdan says:
    August 20, 2014 at 5:48 pm
    “NASA admits they do not know. That should be the headlines. It makes one wonder how much else they do not know..”
    ———————————-
    This admission is very rare indeed, but shouldn’t be. I work with NASA folks (including GSFC specifically) on a VERY frequent basis. Trust me, there is a very large amount of stuff in their assumed areas of expertise about which they are clueless (but that they claim to know). I’m a believer, from my personal experience over 25 years in Aerospace working commercial and government projects, that NASA has over the past two decades or so actually hindered advances in space technology and greatly diminished innovation from what it would have otherwise been. This is what socialism (in this case socialized space under centralized control) does in general.

    I believe that possibly only 10% (or less) of them would actually make it in private industry where constant innovation, efficiency, meeting budgets and schedules, decision-making, taking responsibility, and cost containment matter. The biggest waste I can imagine is giving large sums of money to NASA to accomplish a goal–the sums always get much larger, their behavior drives schedules into oblivion and they fail more often than people seem to remember.

    This organization is not made up of the best and brightest. It’s lots of bureaucrats and technocrats, mostly. We continue to collectively believe in their elite status four decades after NASA led the effort to get twelve men to the surface of the moon and back and the reputation was more deserved. While there are a FEW really great NASA engineers and scientists I’ve worked with, my company has far more talent across all levels. Something must happen to their brains when they put on a shirt with the NASA “meatball” (logo), although some appear able to resist the decay and brainwashing. If any of you fellow s-k-e-p-t-i-c-s believe that climate science is the only discipline within NASA that is biased and backwards, well, you’re being naive.

    Bruce

  26. In addition to unexplained sources of CCl4, the model results showed the chemical stays in the atmosphere 40 percent longer than previously thought.“. Surely, they can’t tell both of these factors from the available data.

  27. Changes in solar activity affect the ozone creation / destruction balance differently at different heights and latitudes within the atmosphere.

    It was never anything to do with CFCs which is why the ozone holes have been recovering whilst the sun became less active much more quickly than was expected at the time of the Montreal Protocol.

  28. Dad had a can of carbon tet before it was illegal. It was covered will skulls and crossbones.

    “NASA admits they do not know. That should be the headlines. It makes one wonder how much else they do not know..”

    The fact that homogenization is a travesty, for one. And with good luck and good management, we’ll make that a headline.

  29. Konrad says:
    August 20, 2014 at 4:00 pm
    ============================================
    To make matters worse with China,s use of the stuff is that some companies have dumped the waste out in the open. That saves a solar panel company the expense of proper disposal. It is a sad state of affairs.

  30. Carbon tet is amazing stuff. If China still makes it they will make LOTS of it because of its uses. If they are claiming to allow the production of 64 units then 640 units are being made.

  31. Is CCl4 well mixed in the atmosphere or not?
    Surely with an ECD it should be possible to sample the jet streams around the globe and determine if the source is marine, Western Europe and the US or China.

    Those seem to be the three options suggested: sea-life, old stuff from waste containers and Chinese industry.

  32. @Boulder Skeptic Yup, NASA has had quite a few screwups. Amazing that only 17 people have died in American spacecraft. The lessons from Apollo 1 didn’t stick. Apollo 13 happened due to two factors. Failure to scrap or repair the oxygen tank after it had been dropped and failure to make sure its electrical system got upgraded when the voltage was increased.

    Amazing that there wasn’t an in flight disaster before Apollo 13! Were any other under spec for the voltage components installed in the service modules prior to #13?

    In 2003, not long before the Columbia disaster, there was a documentary shown on Discovery or History channel about how the Shuttles were serviced between flights. I only got to see part of it and it really showed how out-dated and rife for failure it all was. After Columbia I tried to find the show but it seems to have been effectively tossed down the memory hole. IIRC it was titled “Space Shuttle Garage”.

  33. CFC’s can be produced volcanically. Did no climate scientist think of asking a volcanologist? Oh they would not since volcanologists deal in facts.

  34. <>

    Absolutely, and the production is far to be negligible, (a possible beginning of explanation of the seasonality ?). But man is supposed to be guilty of everything.

  35. “Saw a report a couple of years back where the US (and probably others) military was using it as a degreaser for equipment wash down before maintenance work. Basically pressure washing with the stuff outdoors.”

    And to think I used to feel guilty about using a 400ml can for occasional cleaning of sensitive electronic & mechanical components. Marvellous stuff, it was…

  36. @ Olaf Koenders

    Normally I am in agreement with the vast majority of what you say in your comments; however, your comment is misguided in this case.

    Ozone generally isn’t emitted by industry at all. The ozone forms in the lower levels of the atmosphere when organic chemicals (VOCs) combine with oxides of nitrogen (NO, NO2) and UV radiation from sunlight. Industry DOES emit the VOCs and the oxides of nitrogen. On hot, humid, stagnant days, the industrial emissions sit in one area, get bombarded by UV from the sun, free radical reactions take place, and ozone is formed.

    Since this ozone is in the LOWER LEVELS of the atmosphere, it is a component of smog, and is a bad thing. The Ozone in the UPPER LEVELS of the atmosphere helps to block UV radiation in the first place, and is seen as a good thing.

    Problem is, there is no way of getting the “bad” ozone in the lower levels of the atmosphere up to the upper levels of the atmosphere where the “good” ozone is.

    Now, whether or not ozone in the lower levels of the atmosphere is as harmful as the ALA and the EPA claim that it is is another argument entirely….

  37. @ M Courtney

    A Time of Flight (TOF) Mass Spectrometer would probably be better than an ECD for monitoring at such small concentrations that would be found in the jet streams. Here at ground level the typical “background” concentration that is found in every ambient air sample is 0.07 parts per billion by volume (or 70 parts per trillion if you prefer).

    You could probably use an ECD as well – if you could figure out how to do nearly continuous monitoring using and ECD… with 4 Chlorine atoms attached to 1 carbon, CCl4 would certainly give a pretty strong ECD signal. I think I would still prefer the TOF MS though.

  38. In 1962, the military used it as a degreaser. My fading memory holds that it was banned because of an elevated association with brain cancers?

  39. The thing is, after this ongoing experience with climate alarmism over the last number of years, I don’t trust anything these people say anymore.

    They say that CCl4 lasts 40% longer than previously thought. Where have we heard that before?

    They don’t know where the extra CCl4 is derived. Where have we heard that before?

    They are using Chemistry Climate Model and data from ground-based observations. Where have we heard that before?

    I have almost no trust or confidence in these people at all.

  40. PeterB in Indianapolis says:
    August 21, 2014 at 5:47 am
    @ Olaf Koenders

    Normally I am in agreement with the vast majority of what you say in your comments; however, your comment is misguided in this case.

    Ozone generally isn’t emitted by industry at all. The ozone forms in the lower levels of the atmosphere when organic chemicals (VOCs) combine with oxides of nitrogen (NO, NO2) and UV radiation from sunlight. Industry DOES emit the VOCs and the oxides of nitrogen. On hot, humid, stagnant days, the industrial emissions sit in one area, get bombarded by UV from the sun, free radical reactions take place, and ozone is formed.

    It’s only the near UV that’s involved ~390nm which is absorbed by NO2 which creates O and hence O3.

  41. PeterB in Indianapolis says:
    August 21, 2014 at 5:47 am

    Problem is, there is no way of getting the “bad” ozone in the lower levels of the atmosphere up to the upper levels of the atmosphere where the “good” ozone is.

    Then just how does the 3x heavier CCl4 get up there?

    I never could get my head around the fact that these heavier ‘ozone depleters’ made their way to the upper atmosphere, while the much lighter ozone that was also a ‘pollutant’ hugged the ground and never moved. Never mind the fact that the ‘depleters’ don’t ever seem to ‘work’ anywhere except the upper atmosphere (or the lab).

  42. “CCl4 is still made by China, India and others. No surprise that they are finding the stuff in the air.”

    I thought exactly the same thing and did a Google search using the keywords carbon tetrachloride and China. What they report as produced and used probably bears no connection with reality, just as their GDP figures don’t.

    “NASA admits they do not know. That should be the headlines. It makes one wonder how much else they do not know..”

    With 33 (and counting) excuses for the “pause” given, it’s apparently quite a lot.

  43. There will always be an ‘ozone hole’ in the Antarctic. Ozone is an unstable substance: the ozone produced by the summer sun breaks down into oxygen during the long sunless winter months. The half life of ozone in air at -50C is 3 months, at -35C the half life is 18 days. All this talk of CFCs and carbon tet is just scientist trying to find work for themselves.

  44. mjc says:
    August 21, 2014 at 6:28 am
    PeterB in Indianapolis says:
    August 21, 2014 at 5:47 am

    Problem is, there is no way of getting the “bad” ozone in the lower levels of the atmosphere up to the upper levels of the atmosphere where the “good” ozone is.

    Then just how does the 3x heavier CCl4 get up there?

    Turbulent transport and mixing.

    I never could get my head around the fact that these heavier ‘ozone depleters’ made their way to the upper atmosphere, while the much lighter ozone that was also a ‘pollutant’ hugged the ground and never moved. Never mind the fact that the ‘depleters’ don’t ever seem to ‘work’ anywhere except the upper atmosphere (or the lab).

    The ‘depleters’ like freons and carbon tet are inert in the lower atmosphere, however once they reach the stratosphere they encounter UV light which causes them to slowly break down forming Chlorine atoms which are very reactive and react with O3. The reactions cause destruction of the ozone but the Cl gets regenerated and so a single Cl can destroy as many as 1000 O3 molecules.
    Ozone is an extremely reactive species but there’s no reason why it couldn’t be transported to the stratosphere from the surface, it just won’t make it there intact because it will collide with (and react with) so many other molecules on the way. Typically when the sun rises the reactions start and ozone and photochemical smog are formed, the concentration peaks around noon and after sunset all the O3 is depleted, not enough time for it to make it to the stratosphere.

  45. Gee, its made with methane and chlorine two abundant substances in the atmosphere and oceans.

    CH4 + 4 Cl2 → CCl4 + 4 HCl

    The reaction produces first a hydrogenated chlorides and in excess chlorine, eventually all the “H” reacts to produce carbon tet.

    CH4 + Cl2 =>CH3Cl + HCl
    CH3Cl + Cl2 =>CH2Cl2 + HCl
    CH2Cl2 + Cl2=>CHCl3 + HCl
    CHCl3 + Cl2 =>CCl4 + HCl

    To support this simple ‘model’, there is measurable HCl in the atmosphere, too. This all reeks of NASA’s perplexion over the stubborn ozone hole that is not going away (it waxes and wanes) according to their models. There is a lot of chemistry going on in and on our planet that we don’t yet know about, but this simple reaction should be the first thing they thought about. But then, if they did, they would be raising alarm about the 1.7ppm methane in the atmosphere causing the ultimate destruction of the Ozone sphere. With the abundance of Cl2 in the atmosphere, it is no wonder that methane is so low. If my idea is correct, methane will never be more than a couple of ppm in the atmosphere. One day you will read all about it.

  46. Barrie Sellers says:
    August 21, 2014 at 7:20 am
    There will always be an ‘ozone hole’ in the Antarctic. Ozone is an unstable substance: the ozone produced by the summer sun breaks down into oxygen during the long sunless winter months.

    You have this backwards, the ozone is preserved during the winter, it is in the spring and summer when the UV light from the sun initiates the destruction of the ozone.

  47. Paul Drahn says:
    August 20, 2014 at 3:49 pm

    Paul, you pegged it about right, There are probably thousands (single digit thousands) of these extinguishers still around, but I doubt even a thousand of them still have carbon tet in them. And if every one of the several thousand remaining has 5 pounds of carbon tet in them (unlikely) that amounts to a few tons of carbon tet. That article says something like 39 kilotons of carbon tet is being released every year. Sources like this don’t have a hope of explaining the “unexpected” source.

  48. I vote for China.

    After all, what’s a little ‘carbon tet’ released into the atmosphere compared to adding melamine to milk and baby formula?

    (This based entirely on my ‘gut feeling’, with no basis in fact or information whatsoever.)

  49. Well, there are always been a seasonal “hole” in the ozone-rich layer of polar regions, particularly antarctic because of the strong southerm polar vortex, insulating atmosphere there from the tropical atmosphere during night time (that is months-long night). This has nothing to do with CCl4. The chemical reaction on which this propaganda is based has never been observed in nature either.

    A quick reminder : stratospheric ozone does not protect from the UV, it is merely a byproduct of the absorption of the UV in upper atmosphere by the oxygen there, a very tiny byproduct, very unstable, which exists only because there is UV light reaching the area, breaking down O2 molecules. That is, no oxygen in the atmosphere, no ozone creation process. During winter months, it’s dark over the pole, and that unstable ozone dies out, naturally. Comes the sunrise, october, the polar vortex weakens, and in a matter of days, ozone-rich atmosphere is homogenized again.

    The entire ozone scare was set up and maintained by precisely the same crew that is now running the global warming scam, for the same reason. Check the IPCC origine, it has nothing to do with science. You can wager that by the time the global warming scam has been abandoned, another technology-blaming cult run by these same people will have begun.

    • true
      it seems people always need a scapegoat, whether real or imigined
      however, it could turn out more sinister [eventually]
      like Hitler blaming the jews for everything that was wrong in society.

  50. Phil. says:
    August 21, 2014 at 8:03 am

    Turbulent transport and mixing.

    Fine, but that should work for all gasses…not just the ‘bad’ ones. And most claim that the man-made ‘bad guys’ get up there, but the ‘good stuff’ doesn’t.

    The ‘depleters’ like freons and carbon tet are inert in the lower atmosphere, however once they reach the stratosphere they encounter UV light which causes them to slowly break down forming Chlorine atoms which are very reactive and react with O3.

    And there’s no UV down low?

    We are constantly being told that UV is going to kill us…and last I checked, I’m not living in the stratosphere.

    No. Both ‘theories’ have problems in that they are incomplete. If mixing occurs THEN it has to apply to all gasses not just a select few. Also, UV in the lesser in amount will still have the same properties and the same abilites as it does in the upper.

    Now talking about there being MORE at ground level and the EXCESS, that isn’t afftected by the lower amount of UV being transported by turbulent mixing passes a bit better. But the all ‘bad’/no ‘good’ model does not pass the ‘smell test’…especially given the fact that we are talking about chemistry and not alchemy.

  51. “To investigate the discrepancy, Liang and colleagues used NASA’s 3-D GEOS Chemistry Climate Model and data from global networks of ground-based observations.” Yet again there must be something wrong with reality as the model disagrees with observations.
    I weep.

  52. Mixing does apply to all gases. However, we must also consider chemical reactions.

    Quick chemistry question. What is the color of solid and liquid oxygen?

  53. re cdquarles I think the answer is blue.

    re CCl4 and the ozone layer: the latter seems to have ‘healed’ itself anyway if it was ever ‘sick’ in the first place, but just how much has that caper cost humanity?

    • The ozone layer is healing, but not on its own. Rather it’s entirely as a consequence of the Montreal Protocol, in the US signed by President Reagan and ratified by the Senate, which phased out production of the Chlorine bearing chemicals which caused it — primarily CCL4, CFCs & HCFCs (the primary bad actors) and a few others.

      The industry I worked in during my career – Refrigeration and Air Conditioning, was the primary Global user of CFCs and HCFCs– and the phase-out was costly, but in retrospect worth it, not just because of the environmental benefits in reducing human skin cancer (see the EPA website for quantification, if you want numbers) , but in terms of the superior replacements for HCFCs that were developed by DuPont and other chemical firms. As a result of the industry transitioning to new fluids without chlorine –HFCs — air conditioners gained efficiency, and the stratospheric ozone depletion issue was resolved.

      That ‘caper’ was fully supported by the U.S. A/C and Refrigeration Industry, which voluntarily phased out CFCs one year earlier than required by law.

  54. CH4 + 4 Cl2 → CCl4 + 4 HCl

    Golly, that takes a huge factory and some REALLY hard to get chemicals doesn’t it?

    I mean you can even electrolyse the HCl and get the chlorine back afterwards..

  55. “””””…..Phil. says:

    August 21, 2014 at 8:03 am

    mjc says:
    August 21, 2014 at 6:28 am
    PeterB in Indianapolis says:
    August 21, 2014 at 5:47 am

    Problem is, there is no way of getting the “bad” ozone in the lower levels of the atmosphere up to the upper levels of the atmosphere where the “good” ozone is.

    Then just how does the 3x heavier CCl4 get up there?

    Turbulent transport and mixing……”””””

    Phil; this must seem like a totally dumb question, since IANACh , but it always puzzles me.

    I understand the concept of Chloro-Fluoro-Carbons, eg. “Freons” being rather chemically stable, so they are capable of surviving, long enough, to eventually transport to the Stratospheric levels where uber-UV finally breaks them down, to free the Chlorine.

    But here’s my puzzle. I would have thought that Fluorine would be hell on wheels, compared to Chlorine, when it comes to busting up Ozone. So why is it the Chlorine, and not the Fluorine, that is the bad guy, in the Ozone extermination caper ??

  56. mjc August 21, 2014 at 10:38 am
    Phil. says:
    August 21, 2014 at 8:03 am

    Turbulent transport and mixing.

    Fine, but that should work for all gasses…not just the ‘bad’ ones. And most claim that the man-made ‘bad guys’ get up there, but the ‘good stuff’ doesn’t.

    The ‘depleters’ like freons and carbon tet are inert in the lower atmosphere, however once they reach the stratosphere they encounter UV light which causes them to slowly break down forming Chlorine atoms which are very reactive and react with O3.

    And there’s no UV down low?

    We are constantly being told that UV is going to kill us…and last I checked, I’m not living in the stratosphere.

    The wavelengths needed to photolyze the freons are less than 220 nm, they do not make it past the oxygen through to the troposphere.

    No. Both ‘theories’ have problems in that they are incomplete. If mixing occurs THEN it has to apply to all gasses not just a select few. Also, UV in the lesser in amount will still have the same properties and the same abilites as it does in the upper.

    All gases are subject to turbulent mixing, those that are reactive or condense out at lower temperatures (e.g. water) won’t make it. The UV is filtered by the O2 and O3 in the stratosphere any that reaches the troposphere does not have the same properties as the original spectrum at the top of the atmosphere.

    Now talking about there being MORE at ground level and the EXCESS, that isn’t afftected by the lower amount of UV being transported by turbulent mixing passes a bit better. But the all ‘bad’/no ‘good’ model does not pass the ‘smell test’…especially given the fact that we are talking about chemistry and not alchemy.

    Precisely, it’s chemistry there is no such thing as the ‘all bad/no good’ model.

  57. george e. smith August 23, 2014 at 4:40 pm
    Phil; this must seem like a totally dumb question, since IANACh , but it always puzzles me.

    I understand the concept of Chloro-Fluoro-Carbons, eg. “Freons” being rather chemically stable, so they are capable of surviving, long enough, to eventually transport to the Stratospheric levels where uber-UV finally breaks them down, to free the Chlorine.

    But here’s my puzzle. I would have thought that Fluorine would be hell on wheels, compared to Chlorine, when it comes to busting up Ozone. So why is it the Chlorine, and not the Fluorine, that is the bad guy, in the Ozone extermination caper ??
    Not a dumb question at all George.
    The answer lies in the relative stability of the ‘reservoir’ species that store the released halogens in the stratosphere and allow them to be regenerated after reacting with O3.
    In the case of Cl they are HCl and ClONO2 and for Br HBr and BrONO2, these are weakly bound and so readily generate the reactive intermediates that destroy the O3. F however rapidly forms HF which is strongly bound and therefore sequesters the F and prevents the regeneration of the active intermediates.
    So the effectiveness of the halogens is in the order I, Br, Cl, F: I compounds are too unstable to make it to the stratosphere, Br is about 40 times more effective than Cl which in turn is thousands of times more effective than F.
    Hope that helps George.

  58. Carbon tetrachloride is produced by decaying corpses: “When comparing human decompositional events with animal subsets (pig, deer, dog, cat, squirrel and sheep), carbon tetrachloride, pentane, decane and undecane appear to be human specific, the latter two only when evaluating skeletonized remains.” Vass, Arpad A.: Odor mortis. Forensic Science International. Volume 222, Issues 1–3, 10 October 2012, Pages 234–241. Elsevier.

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