Is Fossil Fuel CO2 Different From Volcanic CO2?

Guest Post by Steven Goddard

Natural CO2 Molecule

CO2 From A Jet Engine

We have all seen lots of pictures of the Eyjafjallajokull eruption now, with steam and ash billowing up in the air. The eruption started one month ago, and as the Guardian reports, The eruption of the Eyjafjallajokull volcano is unlikely to have any significant impact on climate but has caused a small fall in carbon emissions, experts say.

The Guardian editors seem to have forgotten that the volcano itself is spewing massive amounts of CO2 in the atmosphere. Perhaps their kinship with Plane Stupid is having an impact? Plane Stupid’s goal is to stop plane traffic in the UK, and they must be thrilled by the flight ban and the damage to the economy.

Added:
Volcano CO2 budget (CO2 is emitted independent of ash) ~200,000 tons per day X 30 days of eruption = 6,000,000 tons of CO2.

Plane CO2 Budget – assumes half of EU planes haven’t flown for the past six days 340,000 EU tons per day X 0.5 EU shutdown X 6 days = ~1,000,000 tons of savings.

People using alternative transportation (as Anthony and the BBC pointed out) as a replacement for aircraft – cars, trains, battleships , etc. ~1,000,000 tons of extra CO2 Is a battleship more “green” than a jumbo jet?

The total gain is 6,000,000 – 1,000,000 + 1,000,000 = 6,000,000 tons of excess CO2 from the volcano. The temporary aircraft shutdown has little or no net impact on CO2 emissions, but the volcano has a large impact.

Video and reader poll follow.

Below is a video chronology of the glacier and volcano, giving a feel of the events of the past month. First video shows what the glacier looked like prior to the eruption.

The next video shows the first night of the eruption – March 21. Note the similarity to Hawaiian volcanoes – lava fountains and little steam or ash.

By March 24, some steam and ash is starting to appear as glacial meltwater begins to mix with the magma.

By April 14, flash flooding from glacial melt began to pour down the side of the glacier.

The flooding was widespread and devastating downstream.

By April 17, the eruption was primarily steam, CO2 and ash.

Should climate modelers start differentiating between man made CO2 and “organic” natural CO2?

Reader Poll :

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246 thoughts on “Is Fossil Fuel CO2 Different From Volcanic CO2?

  1. [Sarcasm Mode On]

    Volcanic CO2 is far less harmful to the environment because no one makes a profit from it.

    [Sarcasm Mode Off]

  2. I believe they are estimating that the amount of CO2 from the volcano is much less than the CO2 from the planes that would have been flying, and will probably mention the fact that CO2 released high up is different to CO2 released low down.

  3. I have seen reports stating that the volcano is emitting less CO2 than the grounded jets would have.

  4. Walt Meir (sp?) posited on this very blog that there was a unique chemical signature to man made CO2. Willis Eshenbach agreed with him.
    I have yet to see what this secret signature is.
    Could anyone shed any light on this, or are they as I suspect full of the digestive waste products of cattle?

  5. ************
    Alice (07:49:50) :

    I believe they are estimating that the amount of CO2 from the volcano is much less than the CO2 from the planes that would have been flying, and will probably mention the fact that CO2 released high up is different to CO2 released low down.
    ************

    But … but … CO2 is well-mixed, no?

  6. Great poll.

    Your poll reminds me of a question my mother used to ask when when a passel of kids were bouncing through our small house. She’d grab of of us – either me, my siblings, or one of the neighbor’s kids – and ask, “Do you live here or do you ride a bicycle?”

  7. The back-peddling has begun:
    According to the the Guardian’s source (Information is Beautiful) for the amt. of CO2 emitted daily by the volcano, was first quoted at 15K tons/day compared to the total Euro airline industry’s output of 344.1K tons/day. Today the source made a minor correction to its estimate:

    UPDATE 3 – 20th April – : More new info and some shame for us. According to leading geologists, Eyjafjallajoekull is emitting between “150,000 and 300,000″ tons of CO2 a day (source). Despite the attentions of the Icelandic vulcanologists and detailed research, our calculations were apparently off by a factor to 10. Many apologies for this error. The volcano *is* belching huge gobs of CO2 into the atmos. Arguably, still less than the amount that would’ve been emitted by the grounded planes. We’ve corrected the diagram. Thanks to all the commenters who helped us refine and correct our calcs.

    (source: http://www.informationisbeautiful.net/2010/planes-or-volcano/?utm_source=feedburner&utm_medium=feed&utm_campaign=Feed%3A+InformationIsBeautiful+%28Information+Is+Beautiful%29&utm_content=Bloglines)

  8. How much CO2 is the volcano spewing out? You seem to imply you know how much?

    it might make an interesting post to compare thast figure with the daily anthro CO2 emissions…

  9. [Sarcasm mode off]

    Volcanic CO2 is less beneficial to the State than Man-made CO2 because
    they have not (yet) found a way to tax it.

    [Sarcasm mode on]

    (apologies to Mr. Middleton)

  10. Too bad it isnt spewing out as much as the planes. Will mean less tree-growth in the amazonas, and in the deserts.

  11. @Steve in SC (07:56:49) :
    Walt Meir (sp?) posited on this very blog that there was a unique chemical signature to man made CO2. Willis Eshenbach agreed with him.

    Just a guess here… But “man-made” CO2 (actually fossil-fuel-derived) is from carbon that’s been trapped in the earth for a long time. As such, its Carbon-12 to Carbon-14 ratio would be dramatically different from “above the ground” emissions like cow farts. Of course, the CO2 emitted by volcanic eruptions should also have an “older” carbon constituent…

    None of that is actually germane to the discussion at hand, of course. But I have yet to see any discussion of atmospheric C12:C14 ratios that would conclusively indicate what percentage of atmospheric CO2 is actually derived from human activities.

  12. You miss the point.

    Years ago, when I was a practising forester, I would catch periodic hell from various environmentalists (especially in our own organization) when a skidding machine would cross a fish-bearing stream. These crossings were done very infrequently to access otherwise inaccessible portions of harvest units and were strictly limited as to timing, location, and total crossings.

    At one point the same people obtained money to improve fish habitat in some of those same streams and spent one whole summer wallowing down the streams with large track-hoes rebuilding channels and pulling logs into the creeks.

    When I suggested that there was some gross hypocricy afoot, the individual in charge of the projects told me it was not hypocricy because “their hearts were pure”.

    I would suggest, therefore, that you look into your heart (or theirs) when you attempt to criticize your betters.

  13. Even if we would cancel all air traffic for an entire year it would only reduce the the CO2 emissions by a meager 1.5 %. costing the economy billions of dollars a day.

    Air transport is a real soft spot of our economy and security.

    Without it we are back into the Stone Age!

  14. I guess the “bad” CO2 molecules are sad because of all the lies being told about them…

  15. A BBC correspondent pointed out last evening that his attempts to travel back from Helsinki to London weren’t going too well, but that he had calculated the CO2 cost/head of the various boats/trains/cars/etc involved in the whole journey, and found it to be almost identical to the CO2 cost of the flight/head.

    Which is nice to know.

  16. Does Iceland qualify for Carbon credits based on the CO2 not produced by all the planes their volcano halted?

  17. When Katla goes, and it could be soon, this CO2 argument is going to be irrelevant..
    Last Time it erupted big the Mississippi froze north of N.O..

  18. I always pictured natural CO2 as spritely, like a Dryad. It flitters and floats majestically and happily through the meadow, gently feeding the flowers.

    Human-emitted CO2 is a scruffy sketchy guy in a black leather jacket with an illegal concealed handgun. He bullies the other passing molecules and spends most of his days hanging around in downtown areas, mocking and choking the life out of oxygen breathers.

  19. There weren’t any days when EU plane traffic was completely shut down. It was only west of the Alps, so the 340,000 figure is not accurate.

    They are trying to save face, but the 300,000 tons from the volcano probably exceeds the savings from grounded planes. Also, the volcano emissions are just an estimate – with a wide error bar.

  20. Has anyone double checked the figure for the reduction of CO2 from planes not flying? Could they be using the amount “spewed” by all aircraft instead of the amount that would have been “spewed” by the planes not flying in the volcanic ash areas? I have learned to take these things with a grain of salt.

    Don’t you just love the word “spewed?”

  21. Zeke Hausfather (07:58:49) :

    The source that made the original bad estimate is still passing misinformation.

    150,000 is at the very low end of volcano estimates, and the 340,000 figure for the EU is incorrect because only part of the EU was shut down to plane travel. Today the EU is operating at 50%

  22. A rather esoteric concern. Ask a plant and they don’t care where their CO2 came from; all they’ll say is, “Feed me, feed me!”

    BTW, been watching the increase in aircraft flying today in Europe. Must be a bit embarrassing to MET to see those planes overflying the UK with no problems being reported so far, while the UK airports remain closed.

  23. http://www.redorbit.com/news/science/1852153/volcano_co2_output_could_be_150300000_tons_daily/

    Volcano CO2 Output Could Be 150-300,000 Tons Daily

    Posted on: Tuesday, 20 April 2010, 06:40 CDT

    Experts said on Monday that the volcano in Iceland is emitting 150,000 to 300,000 tons of carbon dioxide (CO2) per day, a figure comparable to emissions released from a small industrial nation.

    On a country-by-country basis, the emissions from the volcano would be placed 47th to 75th in the world table of emitters if based on a yearlong output. The data was compiled by the World Resources Institute (WRI), which tracks environmental and sustainable development.

    Being ranked 47th would place it above many other countries including Austria, Belarus, Portugal, Ireland, Finland, Bulgaria, Sweden, Denmark and Switzerland.

  24. I am sure that this is a surprise for the Prophet (aka: Al Gore or El Gordo). He is just an instrumental “freak” who does not know a thing of science and, though profiting relatively a little, is but a puppet of the bankers’ elite who are the real ones behind the scene, as all the policians chore repeating the climate change mantra.

  25. While I voted that there is no difference between the CO2s, I now realize it is a dangerous stance with cap and trade on the horizon. Think of the implications for new revenue sources (taxes) globally if volcanoes are taxed! We must find a way to differentiate the two types of CO2, or pass laws disallowing nations to eject states that happen to have volcanic activity to avoid CO2 taxes.

  26. Has Iceland tried to apply the volcano’s net carbon offset to the carbon exchange market?

    I would imagine that the Gore-Pachauri Alliance might be interested in brokering a deal for the right cut.

    Meanwhile elsewhere, unhappy travelers are venting more than steam by their volcanic reaction to being stranded. (Do extra heavy breaths create additional CO2 that may not have been included in the calculation?)

    ;-)

  27. Is there any estimates as to whether this erution is spewing enough ash into the stratosphere to effect weather in the coming months/years?

    Thanks in advance.

  28. @Alleagra
    “Well, at least the planes aren’t emitting 3,000 tons of sulphur dioxide per day according to this link:”
    Right on! Not to mention all the other nasty things. Isn’t CO2 high in the atmosphere supposed to be worse too. Seems this volcano is super nasty.

  29. Steve in SC (07:56:49) :

    Isotopic composition doesn’t affect chemical behaviour or spectral absorption in any significant way.

    Those properties are controlled by the electron shells, not the number of neutrons in the nucleus.

  30. Regarding the poll…decisions, decisions. I think the Guardian option would be the better choice.

  31. but what about the “other” greenhouse gas being released ? the most significant gas, water vapor, is also being released but as usual is being ignored …

  32. I have the answer!

    Human produced CO2 contains a formerly sequestered carbon with two atmospheric oxygen atoms, decreasing the total amount of free O2 in the atmosphere, O2 that cute deer and rabbits need to live.

    Volcanic CO2 releases formerly trapped oxygen atoms back into the atmsphere, at least once a plant eats it, eventually increasing the number of free oxygen atoms available to deer and bunnies.

  33. stevengoddard,

    I’d say lets just call them equal, since there is enough uncertainty in the volcano emissions (150k-300k) and the avoided flight emissions (somewhere < 340k due to not all flights in Europe being grounded and people taking either trains or cars instead of flights). Probably too much uncertainty to know for sure without putting more effort into figuring it out than the problem really justifies.

    REPLY: Let’s not neglect the fact that when people want to get home, they’ll do whatever it takes. So they shift to other modes of transportation. Many will rent cars (like happened in the USA at 9/11) and drive long distances. Others will move to trains, or perhaps a series of prop driven commuter flight short hops. Of course these produce CO2 also. Whether there’s a net loss of CO2 production overall due to lack of air transportation is certainly debatable. If the volcano continues as it has done in history it will be moot anyway. – Anthony

  34. @R. de Haan (08:07:39) :

    Even if we would cancel all air traffic for an entire year it would only reduce the the CO2 emissions by a meager 1.5 %. costing the economy billions of dollars a day.

    Air transport is a real soft spot of our economy and security.

    Without it we are back into the Stone Age!”

    I dissagree with the Stone Age comment! I believe that most air travel is frivoulous. Tourist dollars would be spent driving to closer destinations, most buisness travel could be done via tele/videoconference. Intra-contenental traffic would just switch to train. The only real impact would be rush shipments.

  35. Anthony captured this image on April 15, which demonstrates just how bogus the 340,000 savings claim is.

    There were planes flying over much of Europe, and the eruption has gone on much longer than any flight disruption. Net effect of the volcano is a large increase in CO2 relative to the planes.

  36. I was the first to vote for ” the world would be better off if there were no CO2″ Just my humble opinion ……so don’t hold your breath. )

  37. I think you’ve asked the wrong question. Volcanos only contribute small amounts of CO2 to the atmoshpere where are regular transpiration and decay of organic matter in the bioshpere is where the bulk of the CO2 comes from. it would also allow you to have cartoon of an old wrinkled carbon in the CO2 if it came from fossile fuel and a new baby carbon (with a passifier) if it came from decaying cellulosic materials.

  38. Don’t forget the ocean acidification. It has already killed all the coral in Kansas. SOX damage is spreading. I am sure we can see all the superstition that is pretend science that erupted during this event.

  39. The options in the poll are not even close to being mutually exclusive. For example, I think that coverage of GW should be scaled down, we need more runways in heathrow, and that there is no difference between MM and NAT CO2. Although you should differentiate it in models if you are trying to ascertain the impact of MM vs NAT. So, your poll is crap. [toungue poke :-)].

  40. debreuil wrote: “Not to mention there is a lot more driving going on.”

    Exactly, and ships being sent by Britian to pick up their stranded citizens, etc. Any comparison of just volcano to planes is missing part of the picture.

  41. “The world would be better of if there was no CO2 1% (5 votes)”

    I’m one of those 5 votes! Just couldn’t pass that up! Of course I also fear Hydronium Hydroxide!

  42. Steve in SC (07:56:49) :

    Walt Meir (sp?) posited on this very blog that there was a unique chemical signature to man made CO2. Willis Eshenbach agreed with him.
    I have yet to see what this secret signature is.
    Could anyone shed any light on this, or are they as I suspect full of the digestive waste products of cattle?

    Steve in SC, the difference is in the 13C/12C isotope ratio. When plants use CO2, they use preferentially 12C (the most abundant), thus the carbon in living and dead (fossil) plants has less 13C, compared to 12C built in.

    Volcanic CO2 is mostly from buried carbonate rocks and/or (sea)water, which has a far higher 13C/12C ratio.

    There is no direct way to make a differentiation between “modern” CO2 from vegetation, directly from decay or indirectly from breathing animals and humans (which have been fed by recent vegetation at low 13C). But there are two indirect ways:

    – the 14C (radiocarbon) content of fossil fuels is essentially zero (much too old), while recent vegetation has some 14C incorporated. This caused radiocarbon dating to use corrections after about 1870, due to fossil fuel burning, but the nuclear tests in the 1950-1960’s caused an extra mess with that.
    – the oxygen use from fossil fuel use can be calculated with reasonable accuracy. This shows a slight deficiency after about 1990. Which means that the whole biosphere (vegetation + animals + humans) produces more oxygen than it uses, thus more CO2 is absorbed than released (about 1.4 GtC/year extra CO2 is absorbed by vegetation) and as that is preferably 12C, this would leave more 13C in the atmosphere.

    But as there is a clear decline of 13C in the atmosphere and upper level oceans, the only source which can cause that is the burning of fossil fuels.
    See the graph made by the late Bert Bolin:

    and the decline of 13C in atmosphere and upper oceans:

  43. CO2 emission from volcanoes are caused by the decomposition of calcite (lime rock) CaCO3+heat=CaO+CO2

  44. gcb (08:07:20) :

    None of that is actually germane to the discussion at hand, of course. But I have yet to see any discussion of atmospheric C12:C14 ratios that would conclusively indicate what percentage of atmospheric CO2 is actually derived from human activities.

    About 6% of the current atmosphere is from the use of fossil fuels, deduced from the 13C/12C ratio. But near the total increase (30%) in CO2 quantity in the atmosphere is caused by fossil fuel burning. Over time, a large part of individual molecules of CO2 are replaced by the seasonal exchanges: these mainly replace CO2, don’t add any CO2, but remove a part of the excess CO2 (about 45% is absorbed by oceans and vegetation, 55% of the emissions remained in the atmosphere as mass, not as individual “human made” molecules).

  45. CO2 and H2O are like your mother and father. The third factor (containing mostly nitrogen) is the spirit of life -religious people (like me) call that God.
    now, if you say your father or mother is bad, what does that say about yourself?

  46. stevengoddard (08:40:19) :

    Steve in SC (07:56:49) :

    Isotopic composition doesn’t affect chemical behaviour or spectral absorption in any significant way.

    Those properties are controlled by the electron shells, not the number of neutrons in the nucleus.

    But Steve, don’t the CO2 molecules with the heavier carbon nuclei settle near the ground and feed plants, while the lighter ones float higher and cause all that damaging warming? Thus whichever source has the lowest ratio of light-to-heavy is the good source, while the source with the highest ratio is the baddest source, pure evil!

    Yes, I’m grinning while I type this. No, I have no idea offhand which has what ratios. Yes, I would grin wider if it turned out that by “gravitational separation” fossil-fuel CO2 was the “good” one. Not that it matters either way except as a source of possible irritation and/or amusement… ;-)

  47. Is Fossil Fuel CO2 Different From Volcanic CO2?

    Yes, sorta: the temps may continue to drop as a result of volcanic eruptions, so (albeit indirectly) that CO2 will have an effect on climate.

  48. Hockey Schtick (08:37:44) :

    According to the unvalidated IPCC computer models, there is a difference between the two sources of CO2:

    http://hockeyschtick.blogspot.com/2010/03/co2-lifetime-which-do-you-believe.html

    HS, the graph compares two very distinct things: the residence time of a CO2 molecule (whatever the origin) is about 5 years, but that is caused by seasonal CO2 exchanges between oceans, vegetation and atmosphere (about 150 GtC over the seasons). That in itself doesn’t add or remove CO2 to/from the atmosphere. The removal rate of the extra CO2 is currently only about 4 GtC/year, thus much slower. The time needed to remove halve of the current 100+ ppmv excess is about 40 years, far longer than the average residence time, but far less than the IPCC model, which includes faster and slower terms, the latter only for a small percentage of the excess.

    Thus you (or Segalstad, where your graph origins) are comparing (sceptic) apples with (IPCC) lemons…

  49. We seem to neglect the amount of ash. Judging by what has fallen on my car – the easiest place to see it – the amount is pretty thin. It’s no more than the occasional Sahara sandstorm blown North. But will it do my garden any good? Will it improve the soil or degrade it? (I live in an acid soil area). Just thinking. Any gardeners out there who might know? (As you might gather, I’m not really concerned about CO2 – this eruption is minor compared to what we might actually get).

  50. There’s absolutely no doubt that reverting to pre-industrial, 18th Century technology would be far far better for all of us. (Well the 2% that Fat Alert & Co. have reflected on their secret ‘Domesday Book of Post AGW Survivors'; understand it’s costs a bit of change and you need the “appropriate” referrals to get into that little booky-wooky.)

    For the 98% of us that won’t be around after the ‘Great Revolution’ it won’t really matter will it? I understand that there’s one heck of an IQ Test given that takes as long as the California Bar Exam (3days), and you have to have the correct genetic makeup –something a little shy of perfectamundo, but not shy by much.

    Well, I guess we should have known; we only had to think about it a minute –when was the last time Big Al and Big Tipper invited us over for a Big BBQ at the Big House?

  51. Some plants, corn for one, prefer C12 to C13 or C14, so coal is deficient in the C13 and C14 percentages.

    So there is a difference

  52. The other night I was watching a Bay Area news program about the snafu with the Iceland volcano and towards the end of the news piece the lady “reporter” perked up and said there is a positive to the volcanic eruption – her comment was somewhere along the lines of “the SO2 emitted by the volcano will cause global cooling to help reduce the recent global warming”. This comment reminded me why I don’t watch the news anymore, or that if I do I need to have a few grains of salt handy.

  53. Grumpy Old man (09:28:27) :

    But will it do my garden any good? Will it improve the soil or degrade it? (I live in an acid soil area). Just thinking. Any gardeners out there who might know?

    I use basalt as addition to the sandy soils in my garden, which is beneficial. In general volcanic ash is quite positive for agriculture (therefore one sees so many people living near volcanoes!). But the Icelandic ones have a nasty extra: quite much fluoride salts, which are poisonous. The local deposits are deadly for animals, but much depend of quantities deposited and the ratio of the different components in coarse and fine dust.

  54. Anthropogenic CO2 has built in GPS so it knows to release energy only at the right time, altitude and direction.

  55. Information is Beautiful, but Correct Information is Even More Beautiful.
    I had a look at the source of the Guardian article, as mentioned in the comment of Sean Peake:

    http://www.informationisbeautiful.net/2010/planes-or-volcano/?utm_source=feedburner&utm_medium=feed&utm_campaign=Feed:+InformationIsBeautiful+(Information+Is+Beautiful)&utm_content=Bloglines)

    They started with an estimate of 7,412 tonnes of CO2 from the volcano, then doubled this value to 15,000 tonnes and now come up with 150,000 to 300,000 tonnes. Now if you would compare the 300,000 estimate with the value of 344,109 for the daily emission from planes, savings in CO2 are less than 13%. Even when taking the average of 150,000 and 300,000 the reduction is less than 35%, not a 60% savings that is claimed in the Figure. Haven’t seen any correction in the Guardian’s post yet (they still stick to the 15,000 tonnes value).

  56. @ Steve in SC (07:56:49) and
    gcb (08:07:20):

    E.M. Smith has a GREAT article about the isotope ratios that “identify” fossil fuels. Which pretty clearly lays out the case that anyone telling you they can conclusively identify that this amount of atmospheric CO2 is man-made by the C12/C13 ratios, is dispensing cow patties.

    Great read, hope you like it too.

  57. T the time of writing this comment, 16 people have voted that the world would be better if there were no CO2.

    So basically then, to those 16 people, the world would be better without life.

  58. Just one small nit to pick Steve:-

    O=C-O , not O=C=O

    Like I said, a small nit.

    And from the top it looks like: O-C=O , not O-C-O

    George

  59. ” kadaka (09:17:29) :
    [...]
    Yes, I’m grinning while I type this. No, I have no idea offhand which has what ratios. Yes, I would grin wider if it turned out that by “gravitational separation” fossil-fuel CO2 was the “good” one.”

    Separating isotopes with gravity or similar forces, namely centrifugal force, is done in those uranium spinners. The best ones of these rotate with speeds close to the speed of sound for months to separate the isotopes.

    So ordinary earth gravity will not do a very good job of isotope separation and its negligible influence will be overwhelmed by any air movement.

  60. The Grauniad seems to be making the assumption that all those poor folks who have been stranded by the ban on flights have remained static and are not producing any CO2 in their frantic efforts to get home and then won’t be producing any when they finally can fly.

    There is already evidence of fleets of coaches being sent across europe to spain to pick up stranded passengers; car travel across multiple countries (eg from Finland to Calais); airliners on standby to make repatriation flights in addition to scheduled flights etc.

    I suggest that when everything has settled down there will have been a significant increase in total CO2, and of course, we are bound to big a leap in global temperatures as a consequence ;-).

  61. “”” enneagram (08:59:11) :

    CO2 emission from volcanoes are caused by the decomposition of calcite (lime rock) CaCO3+heat=CaO+CO2 “””

    That’s all well and good; but isn’t that Limestone Rock itself a fossil, maybe from some ancient ocean sediment ?

    Just asking; seems like volcanic CO2 is fossil fuel effluent to me.

  62. Glad to see that many posters note that the amount of CO2, and not where it comes from is important. Even the much larger Mt Pinotubo eruption in 1991 had no effect on the steady increase of C02 in the admosphere–not even a bump in the monthly data. Volcanoes are more likely to cause global cooling due to effects of dust and aerosols on sunlight (rather than warming due to release of CO2).

    I did not like the poll, because the answer should have been “the amount of CO2 is important, not where it comes from.”

    Bob–You are right that plants show measureable discrimination between carbon isotopes. However, the effects on changes in carbon isotopes on photosynthesis are negligible.

  63. Henry Pool (09:15:13) :What is it evil, then?, obviously what goes against creative laws. And the “evil ones”?, these are of two kinds: those the real evil ones who are conscious of the existence of the real work of universal laws, and nevertheless try to oppose them and promote men’s ignorance and denial of them, as the PNS dark prophet and those just “freaky”, like Al baby, “the Fat One”, who know nothing but who help the real evil ones.
    Evil promotes ignorance and agnosticism.

  64. Zeke the Sneak (09:22:12) : Yes!, both are different: One goes out from a BIG HOLE on the ground, the other goes out from a LITTLE HOLE, back in your car.
    In the US one of the bigger CO2 “manufacturer” is the Yellowstone’s geiser.
    BTW you must challenge EPA to enforce law on it.

  65. Steve in SC (07:56:49) :

    Walt Meir (sp?) posited on this very blog that there was a unique chemical signature to man made CO2. Willis Eshenbach agreed with him.
    I have yet to see what this secret signature is.
    Could anyone shed any light on this, or are they as I suspect full of the digestive waste products of cattle?

    REPLY:
    The short explanation:
    Coal and petrol are Fossil fuels and therefore are supposed to have no C14 left and have lots of C12.

    The long explanation
    It is more complicated than that.
    First they find Coal does have C14 since carbon 12 and 13 are deemed stable while carbon 14 has a half-life around 5700 years give or take a few decades. However they have found radioactivity has caused C14 to be found in coal

    “…In the course of this work, they’ve discovered that fossil fuels vary widely in 14C content. Some have no detectable 14C; some have quite a lot of 14C. Apparently it correlates best with the content of the natural radioactivity of the rocks surrounding the fossil fuels, particularly the neutron- and alpha-particle-emitting isotopes of the uranium-thorium series. Dr. Gove and his colleagues told me they think the evidence so far demonstrates that 14C in coal and other fossil fuels is derived entirely from new production of 14C by local radioactive decay of the uranium-thorium series. Many studies verify that coals vary widely in uranium-thorium content, and that this can result in inflated content of certain isotopes relevant to radiometric dating…” http://www.talkorigins.org/faqs/c14.html

    C-14 is also created in the upper atmosphere by radiation from the sun transforming
    nitrogen-14 into C-14.

    However plants throw a monkey wrench into the whole “man’s signature CO2″

    “…Plant photosynthetic biochemistry is remarkably specific preferring to fix 12C over 13C by a large margin. Thus during photosynthesis d13C rises due to the preferential abstraction of 12C…. Note also that Respiration is Temperature dependent roughly doubling with a ten degree increase in temperature whereas photosynthesis is by and large not temperature dependent. This confounds attempts to correlate temperature with CO2 concentration which in any case cannot be done by simple regression as has been done recently in this discussion. This is because both are measured dependent variables. For regression to work properly one variable must be independent and known.” from jh (06:17:57) :
    See comments near http://wattsupwiththat.com/2010/04/08/nsidcs-walt-meier-responds-to-willis/#comment-364252

    Hope that helps.

  66. Peter Hearnden (08:00:35) :
    How much CO2 is the volcano spewing out? You seem to imply you know how much?

    it might make an interesting post to compare thast figure with the daily anthro CO2 emissions…

    Let’s assume the volcano is emitting the high end 300,000 tons/day:

    http://www.informationisbeautiful.net/2010/planes-or-volcano/

    Human emissions are about 26.4 billion tonnes/year:

    http://www.newscientist.com/article/dn11638-climate-myths-human-co2-emissions-are-too-tiny-to-matter.html

    Per day, that is 72,328,767 tonnes CO2.
    A tonne is 1000 kg – about 1.1 “tons” (2000 pounds).
    So, humans emit about 79.6 million tons/day of C02.

    The volcano is emitting 0.3 million tons/day.
    So, total human emissions are 265.33 times greater, every day.

    If the volcano is actually emitting 150,000 tons/day, then humans are emitting 530.66 times more, every day.

  67. kadaka (09:17:29) :

    Can I play, too??? C14 and C13 are bigger than C12, so, obviously, more surface space for lift. They probably stay in the air longer.

  68. AIR POLLUTION ALERT! Massive amount of carbon dioxide to hit U.S. beginning Wednesday and continue through Sunday!!!!!

    Thursday is Earth Day and beginning Wednesday environmentalists by the thousands will be driving and flying to events everywhere!

    Example: On Sunday, April 25, Earth Day Network will organize a massive climate rally on The National Mall….

    The Climate Rally will include notable speakers Reverend Jesse Jackson, film director, James Cameron, AFL-CIO President, Richard Trumka, Olympic gold medalist, Billy Demong, producer, Trudie Styler, author, Margaret Atwood, NFL player and television personality, Dhani Jones, environmental photographer Sebastian Copeland and many more.

    The Climate Rally will also feature live music from Sting, John Legend, The Roots, Jimmy Cliff, Passion Pit, Bob Weir, Willie Colón, Joss Stone, Robert Randolph, Patrick Stump, Mavis Staples, Booker T, Honor Society and Tao Rodriguez-Seeger.

    Washington DC to be hit the worst!!!!

  69. “”” kadaka (09:17:29) :

    stevengoddard (08:40:19) :

    Steve in SC (07:56:49) :

    Isotopic composition doesn’t affect chemical behaviour or spectral absorption in any significant way.

    Those properties are controlled by the electron shells, not the number of neutrons in the nucleus. “””

    So you are saying (Steve in SC) that Hydrogen and Deuterium have exactly the same Atomic Spectra.

    I believe we can measure frequency differences down to parts in 10^15 or less; I would be surprised if H and D spectra are identical down to that level.

    In fact I believe that actually you are quite wrong, and isotopic spectra are different; and by a darn side more than parts in 10^15.

    As evidence of that I give you the spectrum of mercury, as in mercury vaporlamp sources.

    It is well known that the atomic spectra of 198Hg is quite different from that of raw Mercury. Mercury 198 has spectacularly sharp spectral lines, compared to ordinary common garden variety mercury. I believe it is a lack of some sorts of hyperfine structure that leads to the difference.

    Now I will have to find a photo from some Optics book, that shows the characteristic ring pattern from a Fabry-Perot spectrum of 198Hg, with its nice crisp rings compared to the fuzzy ones from ordinary Mercury.

    198Hg is 10.02 % of natural Mercury

  70. I seem to recall that the two O’s are not at 180 deg from one another, but more like 120 deg.

    The natural CO2 then should have its arms lifted joyously upwards, while the manmade CO2’s arms should hang dejectedly downwards.

    Or is that H2O I’m thinking of?

  71. As far as plants are concerned, has the burning of fossil fuels increased or decreased the available C02 that plants consume, or is it a moot point?

  72. Is it real .. or synthetic

    Organic or Artificial Flavored

    ‘Green’ or dirty brown

    Betcha cant tell it’s not butter

    Is it live or is it Memorex?

    HEy… I know, let’s test it for carcinogens

    We can use my dad’s barn rats!

  73. Ferdinand and others

    Those carbonates in the earth’s crust, that the volcanoes are processing to release the CO2. Weren’t they laid down by living things? I look over to the great chalk hills of southern England. Most of that stupendous mass, hundred of miles long, is in fact sequestered CO2.

    And AFAIK, all of it is the skeletons of tiny sea-creatures.

    And a related question; if plants have an assymetric preference for certain carbon isotopes, how about those sea-creatures?

  74. I just thought of something. Haven’t seen any effigy burnings lately. Is that due to the anti-CO2 sentiment that is prevalent in liberal quarters these days? Or have they just run out of targets?

  75. {The eruption started one month ago, and as the Guardian reports, The eruption of the Eyjafjallajokull volcano is unlikely to have any significant impact on climate but has caused a small fall in carbon emissions, experts say.}

    Hmmmm…. What about this?

    http://ocean.dmi.dk/arctic/meant80n.uk.php

    Coincedence? I think not!

    :)

  76. Howarth (08:50:26) :

    I was the first to vote for ” the world would be better off if there were no CO2″ Just my humble opinion ……so don’t hold your breath. )

    REPLY:
    I take it you do not like to eat… or breathe?

    No CO2 and plants die (under 180 ppm) No CO2 and your body does not know it should take the next breath.

    “The regulation of breathing is a homeostatic control mechanism, meaning that it seeks to maintain the stability of the body’s internal environment via negative feedback mechanisms. For example, high levels of carbon dioxide in the body automatically trigger quicker and deeper breathing, which in turn decreases the level of carbon dioxide by increasing the intake of oxygen…

    Alkalosis. Loss of hydrogen ion in the blood and CSF, leading to respiratory alkalosis, meaning excessive loss of carbon dioxide from the body. An alkaline CSF inhibits the respiratory control center.” http://www.enotes.com/nursing-encyclopedia/breathing-regulation

  77. Peter Plail – you’ve forgotten to factor in the hobo-towns of German Exchange Students discussed in a previous thread here. These new airport-terminal communes may indeed become preferable habitats for some of these stranded travellers. Perhaps some of them have even fine-tuned their tent-mounted solar arrays to better harness the abundant energy put out by the flourescent lighting of JFK International, and not only are completely self-sufficient, but can actually put electricity onto the grid!

    Nothing wrong with that logic. Nope. Somebody slice off a piece of ARRA stimulus funding to subsidize their efforts.

  78. Good discussions of carbon isotopes above, especially by F. Engelbeen. In any case, to summarize, neither volcanic CO2 nor jet-fuel (non-biomass) derived CO2 contain 14C isotope. Their 13C to 12C isotope ratios are slightly different, but practically each is around 99% 12C.

    Should one collect these gases, purify them, add them to water in the same proportions, they both would taste like Perrier (ignoring mineral effects).

  79. Let me get this straight, here is the big dilemna:

    OSLO (Reuters) – A thaw of Iceland’s ice caps in coming decades caused by climate change may trigger more volcanic eruptions by removing a vast weight and freeing magma from deep below ground, scientists said on Friday.
    (Not that we all believe this but for arguements sake…)

    http://wattsupwiththat.com/2010/04/16/we-knew-it-was-only-a-matter-of-time/

    And then we read that large Volcano eruptions cool the earth:

    http://wattsupwiththat.com/2010/04/17/volcanoes-cause-climate-change/

    So can’t we logically conclude then that if man-made greehouse gases causes global warming (at least for this arguements sake), and according to the “Scientific American” global warming causes more volcanic activity, and more atmospheric ash from increased volcanic activity causes global cooling, then global warming causes global cooling and we are right back where we started and we get a vicious perpetual circle.

    (Or maybe natural climate cycles just happen.)

  80. Hockey Schtick (09:45:26) :

    Ferdinand Engelbeen (09:22:37) :

    Please read the file by Dr. Antti Roine at:

    http://hidethedecline.eu/media/AnttiRoine/AnttiRoineSeaWaterCO2.doc

    which shows that the equilibrium curve for CO2 over seawater is far from saturated with no evidence to suggest that we are anywhere near saturation, and explain why this near instantaneous sink is “much slower”.

    The sink rate of CO2 in the oceans and vegetation combined is known with reasonable accuracy: that simply is the difference between what is emitted and what is measured in the atmosphere at the end of the year. We emit about 8 GtC/year as CO2 from fossil fuel burning and we see an increase of 4 GtC/year in the atmosphere. Thus the sink in the oceans is by far not instantaneous, while the sink rate in vegetation includes a lot more factors (sunshine, rain/drought, fertilisers, minerals,…)

    The problem is in the diffusion speed of CO2 in water: that is relatively slow. With a lot of pressure and a small amount of water, one reaches equilibrium quite fast, but for the first 100 meters of the oceans and a small pressure difference, it takes time and for the deep oceans, a lot of time. The surface mixing is even more dependent of wind speed than of diffusion speed and the direction depends of where you are on the oceans (temperature, salt content, biolife,…).

    A lot of knowledge can be found in the work of Feely e.a. at:

    http://www.pmel.noaa.gov/pubs/outstand/feel2331/exchange.shtml

    and following pages.

    Further, the (partial) pressure difference of CO2 (pCO2) between the upper part oceans and the atmosphere is only 7 microatm in average, not 100 microatm (compared to pre-industrial), as the upper oceans already have absorbed a fair share of the extra CO2 and the surface-deep ocean exchanges are limited. Thus compared to e.g. a bottle of Coke, the pressure to push CO2 into the ocean’s surface is about a million times smaller…

  81. Well I actually found a Popular Science article about 198 Mercury. According to that article, 1989 Mercury is made by Neutron bombardment of Gold, in a nuclear reactor. Evidently the first samples of 198 Hg were made this way. The resulting green spectral line is supposedly ten times as sharp as the 643.84696 nm Red Cadmium line which was at the time the Wavelength Standard.

    Given that 198 Hg which is quite stable is 10.02 % of natural Mercury, I can’t figure out why it is so difficult to get. The NBS folks started playing around with 198Hg for standards purposes way back in the 1940s or maybe 50s.

    In any case; bottom line is that different Nuclides most certainly do have different Atomic Spectra.

    So what about CO2 that contains either 12C, or 13C, and also might have 16O or 18O or both.

    So how do different sorts of plants take up CO2 that contains different Oxygen isotopes as well as different carbons ?

    I learned about 198 Hg and its manufacture from Gold in a reactor when I was in University, studying Atomic Physics. Strange to find that Popular Science article after all this time.

  82. George E. Smith (10:12:08) :

    That’s all well and good; but isn’t that Limestone Rock itself a fossil, maybe from some ancient ocean sediment ?

    Just asking; seems like volcanic CO2 is fossil fuel effluent to me.

    Most calcite rocks are calcite deposits from the shells of coccoliths (see http://www.noc.soton.ac.uk/soes/staff/tt/eh/ ) shells are built directly from seawater (bi)carbonate, without altering the isotopic composition of the carbon. Deep ocean water is at about zero per mil d13C, that is the standard used for 13C/12C ratio, based on Pee Dee Belemnite (a carbonate rock) in the early days. Ocean surface water is at 1-4 per mil d13C. Thus carbonate rock deposits are around zero per mil d13C, while organics (fresh and fossil) are around -25 per mil and natural gas can reach -40 per mil.

    For a nice introduction, see:

    http://homepage.mac.com/uriarte/carbon13.html

  83. From DirkH (10:10:29) :
    So ordinary earth gravity will not do a very good job of isotope separation and its negligible influence will be overwhelmed by any air movement.

    Thus you should understand why I’m grinning. I could see that argument being made from a “scientific” basis by others, even though I (and you) know better. “After all, the atmospheric column is very tall so there should be some separation…”

    Although after reviewing the Chiefio’s great article again, I am wondering how the plants are preferably absorbing C12 over C13 by even that small difference. What could be the reason for it?

  84. Gentlemen,

    How much fresh water is being melted by this eruption and where is it going?

    Thinking Ocean, thermohaline circulation/ Great Ocean Conveyor, salt water vs. fresh mixing, and possible impact (if any) on ocean currents that regulate climate…

    Iceland is right in the middle of it too.

  85. George E. Smith (11:03:53) :

    Highly radioactive isotopes are of course going to emit different spectra. That is a different effect from LW absorption by CO2.

  86. Gail Combs (10:20:59) :

    However plants throw a monkey wrench into the whole “man’s signature CO2″

    “…Plant photosynthetic biochemistry is remarkably specific preferring to fix 12C over 13C by a large margin. Thus during photosynthesis d13C rises due to the preferential abstraction of 12C…. Note also that Respiration is Temperature dependent roughly doubling with a ten degree increase in temperature whereas photosynthesis is by and large not temperature dependent. This confounds attempts to correlate temperature with CO2 concentration which in any case cannot be done by simple regression as has been done recently in this discussion. This is because both are measured dependent variables. For regression to work properly one variable must be independent and known.” from jh (06:17:57) :
    See comments near http://wattsupwiththat.com/2010/04/08/nsidcs-walt-meier-responds-to-willis/#comment-364252

    Except that the oxygen balance shows that vegetation is a net sink for CO2, thus not adding any CO2 (as mass) to the atmosphere over a year. All biolife together (slightly) increases the 13C/12C ratio because it is a net sink for CO2. Thus, thanks to the oxygen balance it is quite easy to calculate how much CO2 is absorbed by the oceans and how much by biolife (the “partitioning”). See:

    http://www.sciencemag.org/cgi/content/abstract/287/5462/2467

    and

    http://www.bowdoin.edu/~mbattle/papers_posters_and_talks/BenderGBC2005.pdf

    And I had a comprehensive reaction on your remarks at about 3/4th of

    http://wattsupwiththat.com/2010/04/08/nsidcs-walt-meier-responds-to-willis/

    Even for historic sinks/sources, the d13C rate is also known from ice cores for glacial-interglacial periods and transitions, so it is possible to roughly calculate the relative contributions of oceans and vegetation in the CO2 level changes.

  87. stevengoddard (10:23:38) :

    George E. Smith (10:05:46)

    Hmmm… Wikipedia says differently

    http://en.wikipedia.org/wiki/Carbon_dioxide

    Mr. Goddard is right here, but don’t bother going to Wikipedia…just draw the Lewis dot structures yourself! Can’t go breaking that Octet rule now.

    Regarding
    George E. Smith (10:29:47) :

    You’re right in that the spectra of C12 and C13 CO2 aren’t technically the same. That’s undergrad OChem/PChem. However, Mr. Goddard DID say that he didn’t think they are statistically different, which I think is what needs to be evaluated (anyone have links to spectra?). And since the difference in reduced mass of a C-O bond is ~4.3% for C12 vs C13 (assuming O16), I’d be interested to see if that makes a significant difference.

    Sort of on topic, but a bit OT, can anyone explain to me (or provide an appropriate link) how we’ve not passed the essentially complete saturation of the absorption of IR due to CO2? I would think that just a few dozens of meters of air would have enough CO2 in it to absorb ~99% of the light picked up by the absorption bands of CO2. Thus, any increase in CO2 wouldn’t result in a significant increase in IR absorption, and thus no increase in GHG pickup. So can anyone show me (with molar absorptivities/extinction coefficients and reasonable pathlengths) why I’m wrong?

    Thanks,

    -Scott

  88. “”” Ferdinand Engelbeen (11:05:21) :

    George E. Smith (10:12:08) :

    That’s all well and good; but isn’t that Limestone Rock itself a fossil, maybe from some ancient ocean sediment ?

    Just asking; seems like volcanic CO2 is fossil fuel effluent to me.

    Most calcite rocks are calcite deposits from the shells of coccoliths “””

    Thanks Ferdinand for the info and the link. It will take me a bit of time to figure out just what the H you are talking about; but I will.

    Hey I’ve already lengthened my days out to 37 hours just so I can learn all this stuff you guys post here; it’s not that I have anything better to do while my computer is busily doing my work for me.

    So if I understand your bottom line Ferdinand, Volcanic CO2 from Limestone is a slam dunk different from burnt wood or petroleum or coal ? Or did I not read your numbers correctly ?

    George

  89. kadaka (11:06:17) :
    Although after reviewing the Chiefio’s great article again, I am wondering how the plants are preferably absorbing C12 over C13 by even that small difference. What could be the reason for it?

    Enzymatic affinity at the binding site.

  90. George E. Smith (11:03:53) :

    You’re discussing atomic spectroscopy here (you even use that term). I think everyone else is discussing IR spectroscopy (requires a change in dipole moment from the stretching/bending of a covalent bond). Thus, the effect of isotopic change is much less (though not zero, as it changes the reduced mass).

    -Scott

  91. enneagram (10:15:27) :

    Henry Pool (09:15:13) :What is it evil, then?,Evil promotes ignorance and agnosticism.
    Henry: I agree
    That is why I like WUWT
    it is the best!

  92. kadaka (11:06:17) :

    Although after reviewing the Chiefio’s great article again, I am wondering how the plants are preferably absorbing C12 over C13 by even that small difference. What could be the reason for it?

    The reason is that in biological reactions, form and size matters. The chain of reactions which start to catch a molecule of CO2 and transfer that into hydrocarbons is done by large folded molecules (enzymes if you want) where CO2 (in form and electrical load) fits like a key in a lock. 13CO2 is fractionally larger, thus doesn’t fit that nice in the lock, still occasionally is used, but less frequently (at a slower rate? Don’t know exactly) than 12CO2.

  93. “George E. Smith (10:05:46) :

    Just one small nit to pick Steve:-
    O=C-O , not O=C=O
    Like I said, a small nit.
    And from the top it looks like: O-C=O , not O-C-O

    Actually, I have never seen CO2 depicted as O-C=O, always as O=C=O.

    As a starter, the C will be positively charged (contributed 4 electrons, but participates in only 3 bonds), while the O- part will be negatively charged.

    More advanced is the argument that O=C-O doesn’t respect the symmetry of the molecule (Dooh, where oo is the infinity symbol): CO2 has a.o. a center of inversion, which O=C-O does not have.

    For a full list of the MOs, see http://en.wikipedia.org/wiki/Molecular_orbital_diagram#Carbon_Dioxide_MO_Diagram and click on the diagrams. [1]

    Sjoerd

    Note [1]: I just noticed that http://en.wikipedia.org/wiki/File:MO_Diagram_CO2.jpg has an error: the label MO6 is used twice, while MO7 cannot be found. The lower MO6 (the one next to the MO5) should be MO7.

  94. “”” stevengoddard (10:23:38) :

    George E. Smith (10:05:46)

    Hmmm… Wikipedia says differently
    http://en.wikipedia.org/wiki/Carbon_dioxide “””

    “””
    Hu McCulloch (10:38:55) :

    My bad — Wikipedia http://en.wikipedia.org/wiki/Carbon_dioxide shows the O’s at 180 deg (and, contra George E Smith above, with two double bonds). “””

    “”” Hu McCulloch (10:31:55) :

    I seem to recall that the two O’s are not at 180 deg from one another, but more like 120 deg. “””

    You guys are so slow.

    My molecules were drawn in 3-D

    Z-Axis—> O=C-O rotate 90 about Z; O-C=O

    Steve’s Molecule O=C=O rotate 90 about Z; O-C-O

    Remember the carbon bonds are in the Tetrahedral configuration that forms the DIAMOND LATTICE , so any pair of bonds, is at 90 degrees to the remaining pair; for any possible choice of bonds.
    So the molecule looks like my drawing with one pair seen edge on.

    OK to be fair to Steve, if I rotate MY molecule 45 deg about Z then I DO get HIS molecule with the lines closer together. Hey it’s all fake anyway.

    Steve the reason I draw mine my way, is that it explains why the 15 micron absorption band is two degenerate bending modes which are at right angles.

    So O=C=O cannot easily bend in the plane of the screen because that has to stretch and compress the bond pair; but the side by side pair can both bend in and out of the screen plane.
    Since the two pairs are at right angles (NOT 120 deg), then one pair can flap up and down, while the other pair can flap side to side; giving tow modes which are frequency indistinguishable.

    Like I said Steve it’s a small Nit; but it helps understand why the degenerate pair of identical bending modes in the 15 micron band.

  95. Ferdinand Engelbeen (10:51:24) :”The sink rate of CO2 in the oceans and vegetation combined is known with reasonable accuracy: that simply is the difference between what is emitted and what is measured in the atmosphere at the end of the year.”

    Why is it not equally plausible that CO2 has been rising since the last ice age primarily due to decreasing solubility with rising temperature?

    http://hockeyschtick.blogspot.com/2010/01/co2-levels-in-atmosphere-are-damped-by.html

  96. George E. Smith (11:31:41) :

    So if I understand your bottom line Ferdinand, Volcanic CO2 from Limestone is a slam dunk different from burnt wood or petroleum or coal ? Or did I not read your numbers correctly ?

    George

    Most CO2 from the oceans, rock deposits, volcanic vents,… indeed is around zero per mil d13C, while all organics contain far less 13C, depending of the route that it was manufactured. In quantity, the amounts in (deep) oceans, carbonate rock deposits etc… by far exceed organics (both fresh and fossil). Thus indeed the isotopic composition of CO2 from volcanoes is quite different of CO2 from burning organics…

  97. As a retied vulcanologist, I’m far more interested in the truly nasty molecules that are emitted from this or practically any volcano. We’ll start with arsenic, followed by mercury, then antimony, lead, and cadmium–basically any of the other metallic transition elements found on the periodic chart. Forget about CO2–those environmental soothsayers and hysterical warmers can fret about CO2 all they want, but that’s not the problem.

    Then to balance the other side of the chemical equation for those nasty metals we find the sulfur, which is a major concern, but don’t forget to include others in that group such as selenium, tellurium, and bismuth.

    I’ve only heard them mention sulfur, but there’s a whole range of far nastier things than CO2 in that volcanic brew.

  98. The discussion of CO2 balances seems to ignore the existence of feedback.

    The most interesting thing about CO2 is that its abundance is extremely low. It was far higher long ago but since the evolution of plants and shell forming animals the level has declined dramatically. These life forms die and find there way to the bottom of the sea, trapping CO2 as they do so.

    If you are looking for the causes of climate change, we are just beginners, these guys have been destroying the atmosphere for millions of years! If it were not for volcanos these evil, selfish overconsumers would have killed off almost all plant and animal life long ago!

    Life exists in an abundance that is only just about supportable by the tiny amount of CO2 available. That further implies that there is a long term equilibrium which is normally determined by the limited release of CO2 from volcanos. Since the level of CO2 has apparently been extremely constant over thousands of years it also implies that the biosphere quickly mops up any temporary increase and dies back when levels fall. When I say quickly I mean 100 years or so.

    All the scare stories suggest that extra CO2 will reduce the rate of shell and coral growth but that does not make sense since many of these species evolved and thrived at a time when the concentration of CO2 was higher and temperature was higher too. My guess is that it will not be long before the species that prefer higher CO2 levels will begin to thrive and as they die the rate of CO2 sequestering will dramatically increase. CO2 levels will then fall back to below current levels.

    I wish it were not so because it would be good for us if the CO2 concentration could be kept at a higher level to aid food production but I am afraid this is just a temporary bonus that we should enjoy while we can.

  99. Ferdinand Engelbeen (11:27:06) :
    “…Plant photosynthetic biochemistry is remarkably specific preferring to fix 12C over 13C by a large margin. Thus during photosynthesis d13C rises due to the preferential abstraction of 12C…. Note also that Respiration is Temperature dependent roughly doubling with a ten degree increase in temperature whereas photosynthesis is by and large not temperature dependent.

    The figure you quote for respiration is species dependent and varies by an order of magnitude. It also is observed only for the last few degrees of a particular species growing range. For example, respiration in a C-3 agronomic crop (soybean is my specialty) varies only marginally between ~50 F and ~89 F, but increases greatly from ~89 F to ~92F, where essentially the stomates close and the chloroplasts shut down, resulting in no flux.

    Thus, thanks to the oxygen balance it is quite easy to calculate how much CO2 is absorbed by the oceans and how much by biolife (the “partitioning”). See:

    http://www.sciencemag.org/cgi/content/abstract/287/5462/2467

    and

    http://www.bowdoin.edu/~mbattle/papers_posters_and_talks/BenderGBC2005.pdf

    I’ve never agreed with these papers. Those papers woefully neglect to incorporate ocean biomas in calculations. That would be expected from the educational expertise of the authors.

    1 Department of Geoscience, Guyot Hall, Princeton University, Princeton, NJ 08544 USA.
    2 National Oceanic and Atmospheric Administration/Climate Monitoring and Diagnostics Laboratory, R/E/CG1, 325 Broadway, Boulder, CO 80303 USA.
    3 Institute for Arctic and Alpine Research, and Department of Geological Sciences, University of Colorado, Boulder, CO 80309, USA.
    4 Graduate School of Oceanography, University of Rhode Island, South Ferry Road, Narragansett, RI 02882, USA.
    5 Division of Atmospheric Research, Commonwealth Scientific and Industrial Research Organization, Mordialloc, Victoria 3195, Australia.
    * Present address: Department of Physics and Astronomy, Bowdoin College, 8800 College Station, Brunswick, ME 04011, USA.

    Even they admit that!

    Calculations of interannual variability in land and ocean uptake are probably confounded by non-zero annual air sea fluxes of O2. The origin of these fluxes is not yet understood.

  100. “”” Sjoerd Schreuder (11:48:23) :

    “George E. Smith (10:05:46) :

    Just one small nit to pick Steve:-
    O=C-O , not O=C=O “””

    So Sjoerd, you can join the party above too. Yes I know they are double bonds and the molecule is straight, and they look like my drawing in 3-D, since the four bonds are Tetrahedrally disposed.

  101. Steve, glad someone is bringing some sense to the utterly inane coverage of this in the MSM.

    “The eruption of the Eyjafjallajokull volcano is unlikely to have any significant impact on climate but has caused a small fall in carbon emissions, experts say.”

    That should read self anointed experts. Prof Alastair Dawson has a somewhat different take in his book “So Foul and Fair a Day”.

    http://europe.theoildrum.com/node/6387

  102. “”” stevengoddard (11:40:03) :

    George E. Smith (10:29:47) :

    Here is an interesting article describing the spectral differences of various CO2 isotopic configurations. I do know that climate models do not differentiate between CO2 isotopes in their radiation budgets.

    http://pubs.acs.org/doi/abs/10.1021/ac00284a060 “””

    I’m sure you are right on that Steve; if the climate is sensitive to isotopic differences, then we are all in trouble. I certainly never would imply, that the isotopic differences are enough to flip us over some tipping point; just that the various nuclides are certainly distinguishable from spectral differences.

  103. “Ferdinand Engelbeen (11:41:52) :

    The reason is that in biological reactions, form and size matters. The chain of reactions which start to catch a molecule of CO2 and transfer that into hydrocarbons is done by large folded molecules (enzymes if you want) where CO2 (in form and electrical load) fits like a key in a lock. 13CO2 is fractionally larger, thus doesn’t fit that nice in the lock, still occasionally is used, but less frequently (at a slower rate? Don’t know exactly) than 12CO2.”

    Are you sure that 13CO2 is larger? It goes a bit against my common sense: the size of molecules is determined by their electron cloud, and not by the protons and neutrons directly (indirectly they do as a aresult of the electrical force they apply on the electrons – but there is no difference between 13C and 12C there).

    However, 13CO2 certainly is heavier and thus slower to engage and/or react. As there are a lot of steps before CO2 is captured as some hydrocarbon, a small difference in reaction speed in each step might add up to something measurable.

    So I don’t doubt your conclusion, I’m just a bit surprised by the reasoning.

  104. Scott (11:33:24) :

    You’re discussing atomic spectroscopy here (you even use that term). I think everyone else is discussing IR spectroscopy (requires a change in dipole moment from the stretching/bending of a covalent bond). Thus, the effect of isotopic change is much less (though not zero, as it changes the reduced mass).

    The difference in IR lines is even used to determine the 13C/12C ratio:

    http://cio.eldoc.ub.rug.nl/root/2005/ApplPhysBCastrillo/

    and several others…

  105. Ferdinand Engelbeen (11:41:52)

    How much larger is C13O2 than C12O2? I would guess it’s not larger AT ALL. Sizes of atoms/ions/molecules are governed by the electron cloud. The electron cloud is affected by protons in the nucleus, but not neutrons. Thus, size should not be changed at all.

    Actually, thinking about it a bit more, I wouldn’t be surprised if C13O2 is SMALLER (at room temp) than C12O2, if only by a miniscule amount. That would be because the heavier C13 increases the reduced mass of a C=O bond (by ~4.3%), thus causing that bond(s) to stretch less. The change would be miniscule though, and certainly not enough to affect typical biochemical reactions.

    Any hardcore Physical Chemists want to weigh in? I’d be curious if there is any finite size difference and in which direction that difference is.

    My guess is the reaction difference is kinetic: via the kinetic isotope effect.

    -Scott

  106. Regarding

    George E. Smith (11:51:08) :

    The bonds are NOT tetrahedral, CO2 is definitely a linear molecule. See:

    http://en.wikipedia.org/wiki/Molecular_geometry

    This is well-known, and as mentioned in Sjoerd Schreuder (11:48:23) , this is predicted by VSEPR theory (though it wasn’t called that in the post). Note that, in CO2, carbon is in sp hybridization, not sp3 as in a diamond. This is standard general chemistry level stuff.

    Additionally, even if CO2 were tetrahedral, the bond angles would be ~109 degrees, not 90 degrees. Remember, as you said, this is 3-dimensional. Octahedral structures have 90 degree bonds.

    -Scott

  107. “”” Scott (11:33:24) :

    George E. Smith (11:03:53) :

    You’re discussing atomic spectroscopy here (you even use that term). I think everyone else is discussing IR spectroscopy (requires a change in dipole moment from the stretching/bending of a covalent bond). Thus, the effect of isotopic change is much less (though not zero, as it changes the reduced mass).

    -Scott “””

    Well if you recall this: “”” Steve in SC (07:56:49) :

    Isotopic composition doesn’t affect chemical behaviour or spectral absorption in any significant way.

    Those properties are controlled by the electron shells, not the number of neutrons in the nucleus. “””

    Steve in SC implies that the Nuclear size and mass doesn’t affect the spectra; yet they clearly DO affect the Atomic Spectra; which implies that the energy levels are affected by the nuclear composition.

    And yes I know that the CO2 important absorptions are molecular spectra in the LWIR. The carbon bond lengths, and strengths must be different between 12C and 13C for the same reason the atomic spectra of Carbon are different; and that must make the bending moment of inertia of the CO2 molecule different between those two isotopes. In the end, it is all somewhat academic, since Doppler and Collision (pressure) broadening change all the frequencies anyway.

    And no I don’t think that there are any climate effects from isotopic differences in any constituent of the atmosphere.

    I don’t use Wiki as a reference for anything but Wiki’s opinion on whatever.

    So maybe the Chemists are all mortified that I should draw a double carbon bond edgeways on the show the tetrahedral arrangement; but since I was not contesting the chemistry of CO2; but the Physical prestidigitations of the atoms in the IR molecular vibrations; I don’t particularly care if the Chemists are offended.

    My Fly fishing buddies; would be astonished at the grab success of some of my new molecular “fly” patterns.

    George

  108. Anu (10:22:30) :

    “Peter Hearnden (08:00:35) :
    How much CO2 is the volcano spewing out? You seem to imply you know how much?

    …..If the volcano is actually emitting 150,000 tons/day, then humans are emitting 530.66 times more, every day.”

    SO that is just ONE volcano active at this time. As usual the first rule in science is to formulate the correct question. And you did answer the original question. However there is more than one active volcano.

    Ongoing Activity: | Arenal, Costa Rica | Batu Tara, Komba Island (Indonesia) | Dukono, Halmahera | Karymsky, Eastern Kamchatka (Russia) | Kilauea, Hawaii (USA) | Kliuchevskoi, Central Kamchatka (Russia) | Popocatépetl, México | Rabaul, New Britain | Sakura-jima, Kyushu | Shiveluch, Central Kamchatka (Russia) | Soufrière Hills, Montserrat

    New Activity/Unrest: | Egon, Flores Island (Indonesia) | Etna, Sicily (Italy) | Eyjafjallajökull, Southern Iceland | Gaua, Banks Islands (SW Pacific) | Miyake-jima, Izu Islands (Japan) | Redoubt, Southwestern Alaska | Reventador, Ecuador “ http://www.volcano.si.edu/reports/usgs/

    And then there are the undersea volcanoes: “…The team estimates that in total there could be about 3 million submarine volcanoes, 39,000 of which rise more than 1000 metres over the sea bed….” http://www.newscientist.com/article/dn12218

    “….Currently there are over five thousand active volcanoes underwater varying from ones larger than any on the surface to cones no larger than an automobile….” http://www.crystalinks.com/volcanoesunderwater.html

    So volcanic activity can be a major contributor to the CO2 level depending on the number and size of the active volcanoes.

  109. Hockey Schtick (11:54:35) :

    Why is it not equally plausible that CO2 has been rising since the last ice age primarily due to decreasing solubility with rising temperature?

    http://hockeyschtick.blogspot.com/2010/01/co2-levels-in-atmosphere-are-damped-by.html

    The long term temperature-CO2 ratio (where CO2 lags temperature) is more or less fixed (and surprisingly linear): about 8 ppmv/K:

    The cooling from the MWP to the LIA also did give some 8 ppmv/K drop in CO2 levels.

    Thus even if we assume 1 K warming since the LIA, that wouldn’t give more than 8 ppmv increase in CO2, while we see a 100+ ppmv increase.

    The late Endersbee was completely wrong with his graph: first, what he did was a serious sin in statistics: never compare trends with such a large smoothing (21 years) with another variable (CO2) with far less smoothing (12 months). Second, he compared the last 20 years (with a 21 years smoothed variable!), where both temperature and CO2 go up, while if one extents the graph to 104 years, the correlation is quite different (even negative) in other periods. See:

    As you can see there is a near perfect correlation between accumulated CO2 emissions and CO2 increase in the atmosphere, while the correlation between temperature and CO2 is rather variable. That is also visible in the 1:1 trends:

    and

    where big jumps in temperature have little effect on CO2 levels (about 4 ppmv/K around the trend).

  110. After having been enlightened by a certain congressman from Atlanta I have become worried that this volcano could upset the delicate balance of Iceland thus causing the island to tip over and capsize.

  111. Ferdinand Engelbeen (11:27:06) :

    Furthermore, additional assumptions:

    [9] As noted above, we can use atmospheric O2/N2 data
    to partition anthropogenic CO2 sequestration between the
    land biosphere and the ocean. In its simplest form, this
    calculation assumes that the annually averaged oceanic O2
    inventory is constant. However, this inventory is likely to be
    changing, for two reasons. First, the ocean is warming
    [Levitus et al., 2000], reducing gas solubility and driving
    O2 from ocean to atmosphere [Keeling and Garcia, 2002].
    Second, changes in oceanic stratification may be altering the
    oceanic carbon cycle. These carbon cycle changes would
    likely be accompanied by the transfer of O2 between ocean
    and atmosphere.
    [10] We calculate anthropogenic CO2 sequestration rates
    by the ocean and the land biosphere assuming a constant
    oceanic O2 inventory. We then summarize estimates of the
    rate at which the oceanic O2 inventory is changing, and
    associated changes in calculated anthropogenic CO2 sequestration
    rates. Finally, we examine interannual variability in
    land and ocean CO2 sequestration.

    Also, the randomization of the locations of the sampling sites are obviously a little suspect:

    Station Abbreviation, Station Name ,Latitude, Longitude ,Altitude above sea level, m
    BRW Point Barrow, Alaska, United States 71.32 156.60, 11
    SMO Tutuila, American Samoa 14.24 170.57, 42
    AMS Amsterdam Island, France 37.95 77.53, 150
    CGO Cape Grim, Tasmania, Australia 40.68 144.68, 94
    MAC Macquarie Island, Australia 54.50 158.95, 12
    SYO Syowa Station, Antarctica, Japan 69.00 39.58, 14

  112. Tim Clark (11:56:04) :

    The first remarks weren’t mine, but:

    “I’ve never agreed with these papers. Those papers woefully neglect to incorporate ocean biomas in calculations. That would be expected from the educational expertise of the authors.”

    The oxygen balance is not a simple one, as the year by year noise is quite high, and oxygen level differences are at the edge of analytical possibilities. But in the oxygen and CO2 balance, ocean biomass is included (and is relatively small compared to land biota, if the inventories are accurate). The main problem is the amount of oxygen released/absorbed from simple solubility in seawater (temperature…), which varies from year to year.

  113. Well, first was E.M. Smith’s great article on why detecting an anthropogenic CO2 signature based on atmospheric C12/C13 ratios is bunk.

    Now I have found Dr. Roy Spencer’s article right here on WUWT that lays out about the same.

    BOTTOM LINE: If the C13/C12 relationship during NATURAL inter-annual variability is the same as that found for the trends, how can people claim that the trend signal is MANMADE??

    So I am now up to two trusted sources which tell me that anyone telling me they can find a definite man-made CO2 signature and exact atmospheric amounts based on C12/C13 ratios, is not speaking out of the normal orifice used for transmitting verbal information.

  114. “”” Like in the other arrangements, electrons must be spaced as far as possible. “””

    That is a direct quote from the Wiki molecular shape citation Scott gave above.

    And that is the very reason why the four bonds of the carbon atom are arranged tetrahedrally; because that is the ONLY geometrical configuration that pushes the four electrons as far apart from each other as possible.

    And a Tetrahedron has its four vertices in two pairs which are exactly at right angles to each other. When an Oxygen atom latches on to any pair of those four bonds, we have the two nuclei and the shared electrons in a common plane.
    When a second Oxygen atom latches on to the other pair of bonds; the nucleus of that third atom lies in exactly the same plane at the saem distance forming the linear molecule. BUT the shared electrons for the second oxygen atom ARE NOT in that plane with everything else; but are in a different plane at right angles to the first plane.

    The molecule is still LINEAR as everybody claims (including me) but it is NOT PLANAR

    A Planar Linear CO2 O=C=O looks like this O-C-O, when looked at IN the plane of everything; whereas O=C=O is looking at it PERPENDICULAR to the plane.

    If all four bonds lie in a common plane, then the spacing between the electrons is not maximum; it is maximum when the four bonds are tetrahedrally disposed as they are in Carbon, Silicon, and Germanium; and also alpha Tin I believe. And I suspect their dioxides are all linear but non planar molecules.

  115. Ferdinand Engelbeen (11:27:06) :

    Gail Combs (10:20:59) :

    However plants throw a monkey wrench into the whole “man’s signature CO2″

    “…Plant photosynthetic biochemistry is remarkably specific preferring to fix 12C over 13C by a large margin….”

    Part of the monkey wrench is plants emit CO2 at night AND as E.M. Smith and others noted different plants have an affinity for C12 or C13 and the ratio of those different plant types have changed over time….. I call that a monkey wrench.

  116. Regarding

    George E. Smith (12:22:52) :

    Well clearly “Steve in SC” either wasn’t thinking about atomic spectroscopy or isn’t familiar with it, because of course it’s affected by the nucleus – it’s called atomic spectroscopy. As you’d expect, nuclear magnetic spectroscopy is also affected by the nucleus of an atom.

    However, I contest the idea that the bond lengths/strengths are different for CO2 containing C12 vs C13. The reason their spectra are different is because they have different masses (thus, different reduced mass). Bond length/strength is the “spring” connecting the two masses. In this case, the “spring” is the same, but the masses on the end are different, thus the different spectra. And, yes, it is academic because of the collisional broadening. That was related to why I questioned it in the first place.

    I agree with you about Wikipedia–it’s a piss poor reference (I particularly like to point out Wiki-gate, but you definitely know about that b/c you’ve been on this site for some time). So instead would you prefer me to reference books though? This is general chemistry, so I could reference the book I used for that class or any common OChem/PChem book for that matter. I used Solomon’s “Organic Chemistry” book and Atkins “Physical Chemistry” book, but I don’t remember my Gen Chem book.

    And the chemists are not mortified about rotating molecules, the mortification comes from claiming that CO2 is tetrahedral when it’s linear.

    In the end, none of the above is that important in this thread. However, where it does become important is in the impression left by some skeptics. If I was a newbie to this site and saw you claiming CO2 was tetrahedral, I would be prone to just ignore everything I saw you post in the future, regardless of its merit (or worse, just abandon this site assuming all the people here don’t know what they’re talking about). My expertise is chemistry, so that’s the lens I see things through.

    In reality, I’ve seen a variety of quality posts/thoughts coming from you, so I realize that this is an aberration. However, I’d prefer to see the error corrected so that newbies (or even frequenters) to this site aren’t prone to think we’re full of crap.

    As an example (and Steve Goddard can attest to this), I live in a town with quite a few environmental crazies who have an effect on the general population. Just walking through the CSU campus during a school day gets you attacked by multiple Greenpeace reps. Because of this, people look down on skeptics and if I pointed someone to this site and they saw CO2 being called tetrahedral (and knew better of it), they’d never come back, even if all your other information/comments were 100% valid.

    I’m not trying to pick a fight, just trying to improve the quality of the science discussed here,

    -Scott

  117. Scott (12:04:47) :
    The change would be miniscule though, and certainly not enough to affect typical biochemical reactions.
    Any hardcore Physical Chemists want to weigh in? I’d be curious if there is any finite size difference and in which direction that difference is.

    I don’t think you meant biochemical and then inferred a physical chemist would know. You should ask someone who has had Enzymology; and actually it makes 2.03% difference from corn chloroplasts in one of the most quoted pioneering work (peer reviewed ;~P) :

    Fractionation of Stable Carbon Isotopes by Phosphoenolpyruvate
    Carboxylase from C4 Plants1
    Received for publication September 8, 1976 and in revised form November 22, 1976
    PAUL H. REIBACH AND C. RoY BENEDICT
    Department of Plant Sciences, Texas A&M University, College Station, Texas 77843
    ABSTRACT
    The active species of “CO2″ and the amount of fractionation of stable
    carbon isotopes have been determined for a partielly purified preparation
    of phosphoenolpyruvate (PEP) carboxylase (EC 4.1.1.31) from
    corn (Zea mays) leaves. The rates of the enzyme reactions, using
    substrte amounts of HCO3-, CO2 or CO2 plus carbonic anhydrse,
    show that HCO3- is the active species of “CO2″ utilized by PEP carboxylase.
    The K,. values for CO2 and HCO3- are 1.25 mM and 0.11 mM,
    respectively, which further suggest the preferential utilization of HCO3-
    by PEP carboxylase. The amount of fractionation of stable carbon
    isotopes by PEP carboxylase from an infnite pool of H12C03- and
    H13C03- was -2.03 %o. This enzyme fractionation (A), together with the
    fractionation associated with absorption of CO2 into plant cells and the
    equilibrium fractionation associated with atmospheric CO2 and dissolved
    HCO3- are discussed in relation to the fractionation of stable carbon
    isotopes of atmospheric CO2 during photosynthesis in C4 plants.

  118. nah, you didn’t get it, you see, there is basically 3 types of CO2 molecules:

    – good CO2, the natural one, the one that Gaia send to her plant-children, the volcano one

    – the not so bad CO2, bad, but redempted because it is emmitted for a rightfull cause. The one emitted by Gore jetskis, or Grenpeace boats, or Nicolas Hulot planes. Also the one emitted by any poor (or not too rich) that is on the right frame of mind, i.e. not wanting a better standard of living but wanting to help the children (and make a lot of new ones), or traditional way of living (using fire wood is good, coal or petrol is bad). Basically any emission from non occidental, chinese, japanese or petromonarchy source is ok unless proved otherwise.

    -the really really bad CO2: everything that is emitted by non-green megacorps (green megacorps are ok), by anything related to internal combustion engine or powered individual transportation (except for electric – but this is only temporary), or worse, motorsport, or to individual tourism without the eco or humanitarian excuse. In fact, if your co2 molecule is coming from human activity without the proper contrition, but to improve your material well being, it is really really bad, it makes mother gaia cry….

  119. Sjoerd Schreuder (12:02:42) and
    Scott (12:04:47)

    I stand corrected. I was guessing larger, but in fact it should be somewhat smaller, and kinetics are probably more important in this case than size or form.

  120. Ferdinand Engelbeen (09:13:20) :”About 6% of the current atmosphere is from the use of fossil fuels, deduced from the 13C/12C ratio”

    Are you suggesting that our atmosphere is now made up of 78% N2, 21% O2 and 6% man made CO2?

    Perhaps you meant to say “6% of the CO2 in the atmosphere is from use of fossil fuels”. Since CO2 makes up approx .038 % of our atmosphere, and CO2 from fossil fuel use is 6% of that, the real number would be in the neighborhood of ….. a really, really tiny amount.

  121. George E. Smith (12:50:11) :

    Please go somewhere and read about molecular orbital hybridization. I don’t care if it is Wikipedia, a book, a lecture, or whatever. The bonding around the carbon in CO2 is sp hybridized, and is therefore NOT tetrahedral (which would be sp3 hybridization.

    And don’t quote mine the Wikipedia link I gave. First, WIki is crap, as you yourself say. Second, the quote you gave is for BENT molecules, and CO2 is NOT BENT. Here’s what you should have quoted:

    Linear: In a linear model, atoms are connected in a straight line. The bond angles are set at 180°. A bond angle is very simply the geometric angle between two adjacent bonds. For example, carbon dioxide has a linear molecular shape.

    Just so you know, bent molecules have lone electron pairs on the central atom. Drawing a correct Lewis structure of CO2 shows that it clearly does not have lone pairs.

    And no one ever said that all the electrons were exactly centered between the C and O atoms. Basic general chemistry tells us this! Linear/tetrahedral/octahedral/bent/etc are given by the arrangement of atoms in the system, not the electrons (though the electrons can in fact determine where the atoms go). Saying that you’ve rotated the rod of CO2 to hide some of the electrons doesn’t really work…at the very least the lines in O-C-O should have been bolded in your method (I don’t agree with that, but at least it’s representative of what you’re claiming).

    -Scott

  122. kadaka (12:47:49) :

    Well, first was E.M. Smith’s great article on why detecting an anthropogenic CO2 signature based on atmospheric C12/C13 ratios is bunk.

    I think that E.M. Smith should look at the overall balance: it is certain that more CO2 is absorbed by the biosphere than released. Whatever the pathway, this increases the 13C content of the atmosphere. But we see a decrease, which is only from fossil fuel burning, as all other possible CO2 sources have higher 13C/12C ratio’s than found in the atmosphere.

    Now I have found Dr. Roy Spencer’s article right here on WUWT that lays out about the same.

    BOTTOM LINE: If the C13/C12 relationship during NATURAL inter-annual variability is the same as that found for the trends, how can people claim that the trend signal is MANMADE??

    So I am now up to two trusted sources which tell me that anyone telling me they can find a definite man-made CO2 signature and exact atmospheric amounts based on C12/C13 ratios, is not speaking out of the normal orifice used for transmitting verbal information.

    I do respect both sources, but that doesn’t mean that they can’t be wrong. I responded to Dr. Spencer at the same page, see my comment at:
    Ferdinand Engelbeen (15:37:53) :
    Thus even during natural variations, the d13C decrease from the emissions by far dominates the change in ratio’s, that is why you don’t see a difference between short term and long term variations in d13C.

  123. Tim Clark (13:01:32) :

    I definitely phrased the question that way intentionally. The discussion here already knew there was a preference biochemically (presumably due to the kinetic isotope effect)…what I wanted to know (my own curiousity) was if the C13O2 molecule was slightly smaller than the C12O2 one. Presumably they have the same size at absolute zero, but at finite temperatures I’m hypothesizing that the C13O2 should be smaller due to less stretching of the bond “spring”. Anyone have insight on this?

    -Scott

  124. Gail Combs (12:30:08) :

    Yes, I answered the “original” question. Humans are emitting 265 to 531 times the CO2 from this Iceland volcano if it were to continue for a year. Who knows how long this eruption will last – two weeks ? 1 month ?

    Yes, I realize there is more than one active volcano:
    It is estimated that volcanoes release about 130-230 million tonnes (145-255 million tons) of CO2 into the atmosphere each year. This is … factor of about 100 smaller than the sources from human activity.

    http://en.wikipedia.org/wiki/Carbon_dioxide#In_the_Earth.27s_atmosphere

    If this volcano was at the 300,000 tons/day level, and continued for a full year, that would be 109 tons of CO2. Still less than half of the estimated 255 million tons that might be caused by volcanoes, each year.

    At the high end of 230 million tonnes/year, that is 0.8% of the human emissions for that year. And that doesn’t count “land use changes”, such as cutting down forests for cattle ranching.

    Do you realize “active volcano” doesn’t always mean that volcano is erupting at the moment ?

    http://en.wiktionary.org/wiki/active_volcano

    “…or has the capability of doing so”.
    And even an actual “eruption” can be trivial (first new activity/unrest volcano):

    http://www.volcano.si.edu/reports/usgs/

    a marked increase in seismic activity since 28 March. Small steam plumes normally rose 10 m above the crater.
    10 meter steam plumes are not going to add much to that expected 130-230 million tonnes of volcanic CO2 per year.

    As for the “5000 active volcanoes underwater”:

    http://www.crystalinks.com/volcanoesunderwater.html

    Europe’s largest underwater volcano is active according to the scientists who have been monitoring it for years
    Whoa, sounds ominous.
    There has never been an eruption of the volcano in recorded history.
    Huh. Active, but never an eruption in recorded history.
    A lot less ominous.

    So, for an average year, expect volcanoes to contribute less than 1% of the CO2 that humans emit by burning fuel. Even less, if you count things like burning down forests.

    Of course, if there is ever a really huge volcano, with a VEI of 8:

    http://en.wikipedia.org/wiki/Volcanic_Explosivity_Index

    it might emit more CO2 than humans do that year.
    The last one seems to be about 26,500 years ago, so maybe we’re due.

  125. A comment on d13C excursions.

    A decline of δ13C in the instrumental record is often cited as an “anthropogenic fingerprint” on CO2. The logic being that fossil fuels contain very little 13C and therefore CO2 emissions from fossil fuels is diluting 13C relative to 12C.

    This line of reasoning is totally fallacious. δ13C declined sharply in the early Holocene. It pretty well declines whenever CO2 levels rise. Here is just one example of many…

    A distinct δ13C decline in organic lake sediments at the Pleistocene-Holocene transition in southern Sweden
    DAN HAMMAKLUND 1
    1 Department of Quaternary Geology, Lund University, Tornavägen 13, S-223 63 Lund, Sweden
    Copyright 1993 Collegium Boreas
    ABSTRACT
    Values of δ13C obtained from conventional bulk sediment radiocarbon dates encompassing the Pleistocene Holocene boundary have been compiled and plotted against 14C age. In all. 286 lake sediment dates from southern Sweden in the range 8.000 to 13.000 BP have been evaluated. A significant decrease in δ13C values, initiated shortly before 10.000 RP and amounting to 5%, is distinguished. This change is accompanied by increased limnic productivity. decreased erosive input and increased organic carbon content of the sediments. A probable explanation for the δ13C decline in organic material is decreased importance of dissolution of silicates at the transition to the Holocene. During the Late Weichselian. extensive weathering of exposed minerogenic material with subsequent input of bicarbonate to the lake water may have caused a relative enrichment of 13C in dissolved inorganic carbon. Furthermore, the early Holocene increase in terrestrial vegetation cover probably led to an increased supply of 13C depleted carbon dioxide to the lake water by root respiration. Altered limnic vegetation, presumably towards increased production of phytoplankton. could also have contributed to the observed decreasing δ13C trend. The importance of these processes compared to other possible influencing factors. mainly endogenic carbonate production and changes in the global carbon cycle. is discussed.

    LINK

    Here’s an example from early Holocene speleothems…

    Delta 13C values were high until 17.79 ka after which there was an abrupt decrease to 17.19 ka followed by a steady decline to a minimum at 10.97 ka. Then followed a general increase, suggesting a drying trend, to 3.23 ka followed by a further general decline. The abrupt decrease in δ-values after 17.79 ka probably corresponds to an increase in atmospheric CO2 concentration, biological activity and wetness at the end of the Last Glaciation…

    LINK

    There is an overwhelming body of evidence that δ13C has declined when over all CO2 levels have risen. This was the case long before Colonel Drake drilled his first oil well near Titusville, PA in 1859.

  126. Tom in Florida (13:23:28) :

    Perhaps you meant to say “6% of the CO2 in the atmosphere is from use of fossil fuels”. Since CO2 makes up approx .038 % of our atmosphere, and CO2 from fossil fuel use is 6% of that, the real number would be in the neighborhood of ….. a really, really tiny amount

    Sorry for the confusion, indeed, 6% of the CO2 in the atmosphere still is of human origin, not 6% of the atmosphere…
    But that doesn’t change the fact that humans are responsible for near the full increase (30%) of CO2 in the atmosphere, but most of the “human” CO2 molecules were replaced by (deep ocean) natural ones over the years.

    It can be compared to the difference between the turnover and the gain of a factory: in this case human CO2 is only a small part of the turnover, but fully responsible for the gain, as the emissions are about twice the gain. Without the emissions, there would be a net loss, whatever the size or frequency of the other transactions.

  127. Environmentalist Wacko Credo:

    From Gaia all blessings flow. CO2 emitted by Gaia is natural, a blessing.

    If Man, in Hubris, seeks to imitate our God, Gaia, emitting CO2, then his act is an abomination.

    Gaia will punish Abominable Man with Terrible Events….Hurricanes, Earthquakes, Volcanos. (Just ask Danny Glover).

  128. Tim Clark (13:01:32) :

    I don’t think you meant biochemical and then inferred a physical chemist would know. You should ask someone who has had Enzymology; and actually it makes 2.03% difference from corn chloroplasts in one of the most quoted pioneering work (peer reviewed ;~P)

    The story doesn’t determine what caused the fractionation in the ultimate enzymic reactions (interesting that it is the bicarbonate ion which is mainly used). The first fractionation at the air-water boundary indeed is a matter of kinetics (the same happens at the air-ocean border in both directions), but as for many biochemical reactions size and 3D-structure is important, I still wonder if that also is the case for 13CO2 vs. 12CO2 incorporation.

  129. Here’s a new show CNBC is airing TONIGHT called:

    CARBON HUNTERS (First showing TONIGHT: April 20, 10pm (EST-US)):
    Making Money Out Of Thin Air
    CNBC takes a revealing look at the booming, lucrative and often bizarre world of carbon trading.

    ABOUT THE SHOW
    As corporations, governments and consumers hunt for ways to reduce and offset their greenhouse gas emissions, a whole new breed of businessman has been born. Welcome to the world of the Carbon Hunters. They are scouring the planet in search of new ways to capture carbon; lassoing every dime they can, often with shams and scams that make our heads spin. They then are trading the resulting – and often lucrative – credits.

    Many believe carbon trading is a process vital to stopping climate change. And just as many are skeptical. What’s not debatable is that carbon offset trading is emerging as one of the century’s biggest business, political and environmental stories. But behind the carbon credits on an airline ticket, shares in a tree-planting scheme or a project that will supposedly suck carbon out of the air, lies a tale of dubious truth which can bring disaster to both the poor and the investors and people in the developing world.

    Carbon Hunters follows Vancouver-based businessman Shawn Burns and other hunters around the world, as they seek out new and interesting opportunities such as methane capture projects in the Philippines, carbon exchange houses in Mumbai and Chicago and the golden wheat fields of Alberta, in the world’s first regulated carbon market.

    It’s a curious, burgeoning industry that is changing the nature of business – and one that, depending on who you believe, just may help save the planet.

    paullm – Previously, I’ve found CNBC to be Green biased. I’ll check them out tonight and see if that continues to be the case. There should be multiple viewings in the AM and in the future.

    For brevity I am deleting the additional listing of other shows which you can see by visiting the CARBON HUNTERS website (www.cnbc.com/id/35872593/).

  130. Ferdinand Engelbeen (09:13:20) :

    “About 6% of the current atmosphere is from the use of fossil fuels, deduced from the 13C/12C ratio. ”

    Is 6% correct as CO2 is about 380 ppm which is about 0.03%? With 21% Oxygen and 78% Nitrogen all the other gases are part of the remaining 1%. I suspect your 6% was a typo?

  131. “George E. Smith (13:19:13) :

    http://www.chem.ucsb.edu/coursepages/05spring/1C-Perona/hybridization.pdf

    Which uses the VSEPR model. Which is a *model* that works most of the time, but is not exact. LCAO is better, but requires much more calculations.

    Luckily, VSPER is good enough for most applications. That’s why students usually are taught the VSEPR model first. Only those that specialize in theoretical chemistry go on and study the better methods.

    More correct is it to look at all atoms at the same time, form symmetry adjusted atomic orbitals, and recombine them into molecular orbitals.

    VSEPR only looks at pairs of atoms in a molecule. It acts like one C=O bond is totally independent of the other C=O bond. VSEPR typically falls apart for benzene like structures, where bonds are not localized between two atoms but smeared out over the molecule.

    The difference here comes down to this: one of the lone pairs on one O lies in the same plane as the double bond between the C and the other O, and interacts with it. The interaction is such that the bonds is lengthened to cover all three atoms. In fact, LCAO shows us that the two Os cannot be told apart anymore: their p-orbitals contribute equally to each bond!

    Both ‘extended double bonds’ have the same energy and are degenerated. As a result, any linear combination of the those two is also acceptable. Generally speaking: A’ = A*cos(phi) + B*sin(phi); B’ = -A*sin(phi) + b*cos(phi).

    Only by breaking the symmetry, e.g. applying an external electromagnetic field or bending the molecule, the two bonds are split up. And yes, that has implications for the IR spectrum of CO2. But the bonds stay extended: One will be on the inside/outside of the bended molecule, the other will be perpendicular to bending. You still won’t be able to differentate between the O atoms.

  132. We, “Humans”, nothing but oxygen breathing microscopic molds, living on molten lava slag which we call ground, and which crystallizes as mountain chains and cools also as amorphous powdery lands, could we even allucinate we can control environment?
    Ask AL the Magnificent and their followers of the Gaia Cult just to try to shut that smokey iceland volcano, of unpronounceable name, as a demonstration of their prodigious intelligence!

  133. From various Industry spokesmen, including engineers and pilots, interviewed on Auntie Beeb’s 10:00pm news tonight, it would appear that the consensus (THAT word again!) is that the ash scare has been very over-blown. Most seem to think that the closing of the airspace to flight over the UK was an error.

  134. cal (11:56:02) :

    The discussion of CO2 balances seems to ignore the existence of feedback….

    Cal, nicely put. I find it very interesting that plants love “high” levels of CO2 around 1000 ppm. At 200 pm CO2 trees starve.

    My take of the situation is that mankind in burning fossil fuel is liberating much need CO2 into the environment. The fact that limestone, tar, coal, peat, and petroleum are all byproducts of the biosphere makes them part of nature and mankind is returning much needed components back into the active cycle. Sure beats starving people and animals because CO2 is limiting plant growth.

  135. David Middleton (13:39:50) :

    A comment on d13C excursions.

    A decline of δ13C in the instrumental record is often cited as an “anthropogenic fingerprint” on CO2. The logic being that fossil fuels contain very little 13C and therefore CO2 emissions from fossil fuels is diluting 13C relative to 12C.

    This line of reasoning is totally fallacious. δ13C declined sharply in the early Holocene. It pretty well declines whenever CO2 levels rise. Here is just one example of many…

    David, the increase of d13C from the last glacial maximum to the start of the Holocene in the atmosphere was about 0.4 per mil, with CO2 increasing from about 180 to 260 ppmv. See:

    http://epic.awi.de/Publications/Khl2004e.pdf

    During the Holocene, CO2 levels slightly increased to about 280 ppmv, while d13C levels remained stable at -6.4 +/- 0.1 per mil. See:

    Since about 1850, d13C levels in the atmosphere decrease from -6.4 to currently -8 per mil, while CO2 levels increased from about 280 to near 390 ppmv.

    Not only is the change in d13C far larger than ever seen in the past, but completely opposite in trend (but in ratio to CO2 emissions…) compared to CO2 increases during glacial-interglacial transitions.

    d13C levels in lake sediments and speleotherms are locally influenced, and can’t be used for global estimates.

  136. Gail Combs (14:17:48) :Sure beats starving people and animals because CO2 is limiting plant growth
    But it is precisely that what Al Baby wants, to limit the number of births among those smelly and working commoners and make possible the chosen ones only to survive, those brilliant minds as He himself, the supreme green kool-aid drinker.

  137. @Scott (13:01:15) :

    Ah, Atkins… We used that one for Physical Chemistry as well.

    As for a reference: Sorry, I can’t find my old books anymore. It has been 15 years since I studied chemistry, and I’ve been working in ICT since. The books are stored somewhere, but I don’t recall in which box. :(

    Searching for ‘LCAO’ (Linear Combinations of Atomic Orbitals) or ‘Hartree-Fock’ might yield something, but at first glance I can’t find an introductional piece. Maybe http://www.chem.qmul.ac.uk/software/download/mo/ but it seems to cut too many corners to be really useful.

  138. Steve in SC (07:56:49) :
    Walt Meir (sp?) posited on this very blog that there was a unique chemical signature to man made CO2. Willis Eshenbach agreed with him.
    I have yet to see what this secret signature is.
    Could anyone shed any light on this, or are they as I suspect full of the digestive waste products of cattle?

    Folks assert this is true. It isn’t. The basic problem is that “fossil” C has a wide range of C12 to C13 ratios in it. That, and we have no idea how much of the CO2 that comes from things like, oh, Volcanos and natural gas seeps and natural coal fires has which C12/13 ratio / signature.

    Until and unless you measure the c12/13 ratio at volcanoes all over the world (and that includes the mid ocean ridges we can’t quite sample well enough…) AND all the natural gas, oil, and coal seeps / fires AND all the soil sources… until that day, you are just making stuff up.

    After that day you get to figure out what the ratios were for all the oil, coal, and natural gas we’ve already burned. Realize that the ratios are different for each source and that, by definition, we’ve burned up the source…

    And for all the folks talking about plants having preferential absorption of different isotopes remember that C3 vs C4 plants have different enzyme systems and thus different ratios. So you also get to figure out the historic ratio of these two plant metabolism types. For bonus points you get to figure out how both have evolved over time AND how both work in a differential way at different concentrations of CO2 and with different atmospheric ratios of C12, C13 and even C14 just for fun…

    After that, you get to figure out what ratio of c12 to c13 was in all the sequestered stuff under the ice age glaciers and how THAT was released into the air over time during the start of the interglacial…

    The bottom line, IMHO, is that the c12 / c13 ratio metric is substantially unusable as we simply do not have the needed data (and most likely can never get it.)

    (Link to the detailed article was in a comment above)

  139. H.R. (07:58:12) : Your poll reminds me of a question my mother used to ask when when a passel of kids were bouncing through our small house. She’d grab of of us – either me, my siblings, or one of the neighbor’s kids – and ask, “Do you live here or do you ride a bicycle?”

    Friends dad: “Do you walk to school or bring your lunch?” ;-)

    (My smart mouth answer: Yes. (being aware of xor vs inclusive or…)

  140. C. Bruce Richardson Jr. (08:24:27) : Don’t you just love the word “spewed?”

    It’s one of those irregular verbs:

    I enlighten, you pontificate, he/she/it spews

    (With apologies to “Yes Minister” ;-) from whom the original originates )

  141. “”” Sjoerd Schreuder (14:10:02) :

    “George E. Smith (13:19:13) :

    http://www.chem.ucsb.edu/coursepages/05spring/1C-Perona/hybridization.pdf”

    Which uses the VSEPR model. Which is a *model* that works most of the time, but is not exact. LCAO is better, but requires much more calculations.

    Luckily, VSPER is good enough for most applications. That’s why students usually are taught the VSEPR model first. Only those that specialize in theoretical chemistry go on and study the better methods. “””

    Sjoerd, thanks for the details; you need to know that my formal Chemistry stopped at High School, and included virtually zero Organic Chemistry; so I take a somewhat simpler stick in the sand approach to some of these problems; so I visualize the C atom as a ball with four springs sticking out in a tetrahedral configuration, that I can bend over to make double or triple bonds with some other “ball”. That naturally leads to two pairs of shared electrons which are at right angles (the pairs) in a linear CO2 molecules. And yes I know that at the atom level all those electrons are in different orbitals that complicate the configuration of molecules. A completely planar configuration would make the two degenerate bending modes of the 15 micron CO2 band seem untenable.

    Here’s the animation I was looking for.

    http://science.widener.edu/svb/ftir/ir_co2.html

  142. Jeff in Ctown (Canada) (08:39:35) : The last time this volcano erupted, it lasted for 18 months. If that hapens this time, what will happen to Europe/air industry?

    Also realize that most of the time that THIS volcano goes off, about 2 years later the bigger one that shares the same magma system goes off.

    We are only at the start of this puppy. In about 2012 (Gosh!) the Big Dog goes. (IFF past is prologue …)


    Zeke Hausfather (08:43:58) : I’d say lets just call them equal, since…

    REPLY: Let’s not neglect the fact that when people want to get home, they’ll do whatever it takes. So they shift to other modes of transportation. Many will rent cars (like happened in the USA at 9/11) and drive long distances. Others will move to trains, or perhaps a series of prop driven commuter flight short hops. Of course these produce CO2 also. Whether there’s a net loss of CO2 production overall due to lack of air transportation is certainly debatable. If the volcano continues as it has done in history it will be moot anyway. – Anthony

    AND don’t forget that just sitting there is a ‘carbon maker’. You must be kept warm, fed, washed, informed, etc. And the hotel room needs to be cleaned and the dishes and sheets washed and the staff hauled to and from work.

    The “first approximation” metric is simply cost. Energy and embodied energy is a large part of the cost of everything. So, air fair to Chicago: $300. Cost of food and lodging in a decent hotel once there: $200 / night. Low end $100. Rough first estimate: If you lose 2 to 3 days waiting for a flight in a hotel, you have made more CO2 than getting home. Double it for an error allowance and you are still at 6 days max. Now, spend those 6 days on the road in cars, trains, busses, etc AND nights in hotels trying to get home…

    The simple fact is that it’s best to have the least cost solution and that least cost solution is a fast flight home ON TIME and ON SCHEDULE.

    Both for cost and for CO2 “generation”.

    bob (09:30:13) : Some plants, corn for one, prefer C12 to C13 or C14, so coal is deficient in the C13 and C14 percentages.

    So there is a difference

    Corn, being a grass, is C4 metabolism. Most non-grasses (but not all) are C3 metabolism. You need to know the ratio of those two plant types to get the total sequestration ratio right. Also the historic ratio to get the total “natural” release right from soils et.al.

    But the bigger problem is that not all fossil fuels are created equal. Each has a different (and rather wide ranging) ratio. It’s that bit which is most often ignored…

    Oh, and are you REALLY sure that the mid ocean ridge CO2 ratios are the same as those from subduction volcanos? Really really sure? AND they always have been?…

  143. E.M.Smith (14:51:55) :

    While you are right about the very different d13C ratio’s plants and fossils have, the essence is that since about 1990, the oxygen measurements are able to detect approximately how much O2 is used or released by the total biosphere.
    While the O2/N2 ratio determination is quite difficult, one can safely assume that the total biosphere is producing oxygen, thus absorbing more CO2 than releasing it and preferably 12CO2. Thus it is not important at all to know all the different streams in different plants with their different d13C levels: the biosphere as a whole is a source of 13C, not a sink.

    The only exception is natural methane. This hardly influences the CO2 levels (after oxydation) but may have a stronger impact on d13C levels. But if we look at the previous interglacial, the natural CH4 level was about 700 ppbv. Even with a short about 10 years lifetime, that has little impact on d13C levels of the past. The current 1800 ppbv may have more impact, but as most of that is also human induced, that adds to the human impact on d13C levels.

    Similar for near all other CO2 sources: these would increase the d13C levels of the atmosphere when huge quantities would be released: (deep) oceans, volcanic vents and eruptions, calcite rock weathering,…

    At last fossil fuels. While the different d13C levels of different fuels are more or less known with large margins of error, that is not important. What is important is that all fossil fuel use (and land use changes and methane releases) together decreases the d13C level of the atmosphere (and the ocean surface). This simply adds to the many observations that humans are fully responsible for most of the CO2 increase.

    d13C levels and oxygen levels only make it possible to determine what the partitioning is between the two main natural CO2 sinks: oceans and biosphere, with large margins of error. But what is most important is that nature as a whole is a net sink for CO2, whatever the partitioning.

  144. enneagram (14:12:33) :
    We, “Humans”, nothing but oxygen breathing microscopic molds, living on molten lava slag which we call ground,

    You should try moving to a new neighborhood, or getting new friends…

  145. What the plane-haters fail to realise is that, per passenger/km, a 747 is midway in the fuel-efficiency figures between cars, buses and trains.

    Boeings figures show a fully-loaded 747 getting 100 miles per gallon per passenger. To get the same efficiency with a passenger car, you’d have to have two adults in a 3 cylinder diesel mini car returning 50 mpg. I doubt many of the people driving all over Europe are doing it in economy cars, or buses, and I believe the trains are all full.

  146. “”” Scott (13:25:04) :

    George E. Smith (12:50:11) :

    Please go somewhere and read about molecular orbital hybridization. I don’t care if it is Wikipedia, a book, a lecture, or whatever. The bonding around the carbon in CO2 is sp hybridized, and is therefore NOT tetrahedral (which would be sp3 hybridization.

    And don’t quote mine the Wikipedia link I gave. First, WIki is crap, as you yourself say. Second, the quote you gave is for BENT molecules, and CO2 is NOT BENT. Here’s what you should have quoted:

    Linear: In a linear model, atoms are connected in a straight line. The bond angles are set at 180°. A bond angle is very simply the geometric angle between two adjacent bonds. For example, carbon dioxide has a linear molecular shape.

    Just so you know, bent molecules have lone electron pairs on the central atom. Drawing a correct Lewis structure of CO2 shows that it clearly does not have lone pairs.

    And no one ever said that all the electrons were exactly centered between the C and O atoms. Basic general chemistry tells us this! Linear/tetrahedral/octahedral/bent/etc are given by the arrangement of atoms in the system, not the electrons (though the electrons can in fact determine where the atoms go). Saying that you’ve rotated the rod of CO2 to hide some of the electrons doesn’t really work…at the very least the lines in O-C-O should have been bolded in your method (I don’t agree with that, but at least it’s representative of what you’re claiming).

    -Scott “””

    Well I did go here:-

    http://www.chem.ucsb.edu/coursepages/05spring/1C-Perona/hybridization.pdf

    And I did go here:- http://science.widener.edu/svb/ftir/ir_co2.html

    I didn’t find anywhere that showed all the shared electrons being in the same plane as the linear nuclear configuration of the three atoms; and if they were then the 15 micron bending mode would not those two forms.

    But I’ll gladly take your word for it that everything is in the same plane.

    As for the quote I cited from your reference: “”” George E. Smith (12:50:11) :

    “”” Like in the other arrangements, electrons must be spaced as far as possible. “”” That was in fact in part of the wiki article that at the time was talking about H2O which IS a bent molecule; BUT the quote does say “Like in the other Arrangements,” so it was not restricted to bent molecules.

    And as for this “”” And no one ever said that all the electrons were exactly centered between the C and O atoms. Basic general chemistry tells us this! “””, please note that “no one” also includes ME among those who have never said that.

    I’ll accept your statement that linear, tetrahedral, etc refers to the atom configuration, and not the electron configuration; and given that I certainly am and always have been in agreement that CO2 is a linear molecule; and that I was making an mistake by erroneaously using the term tetrahedral to refer to the carbon atom bonds; which result in a tetrahedral atomic configuration in the diamond crystal.

    I’m always happy to learn and to learn to not use technical terms in the wrong context.

    I’ll just assume that the little CO2 animation above is fictional; and that CO2 doesn’t really do that at 15 microns (well it only does one of those two bending vibrations)

    My Keyboard only has a choice of = or – and there is no bold shift key to change either of them to something else. It just seemed natural to me that a 90 degree rotation turns = into -; but then since that isn’t the real structure anyway; then that becomes superfluous.

    So my apologies to Steve for suggesting his happy faces weren’t quite correct.

  147. George E. Smith (15:11:41) :

    Apologies if I went overboard with my explanation. It has been a long time since I studied theoretical chemistry but I still like the subject. As a result, I might have become a bit too enthousiastic. (And I’m a bit surprised the mods let it all through – this will be my last on this subject)

    As Scott wrote at 13:01:15: Details like this might make a casual reader with a chemical background reject your other, valid points.

    There is no harm in visualizing CO2 with balls-and-sticks for yourself, as long as you remind yourself that it’s just a model. It’s ‘good enough’ for most cases, and a very successful model at that.

    As a chemist, I don’t see any problem writing H-O-H for water, or H3C-CO-CH3 for aceton, even though I know that both are bend. Thanks for showing me which assumptions I unconsciencely make :)

    In fact, you can forget most everything I wrote. As long as you remember that the 3D situation usually is too complex to show in a 2D drawing, so chemists just use O=C=O and don’t care whether it is a correct projection of the 3D situation – it usually isn’t. It shows which atoms are connected, and whether bonds are single or double – and that’s all it says to a chemist.

    BTW, nice animations of the various vibrational modes.

  148. Hey Anthony, not bad for a “mere” meteorologist to have so many unbelievable scientific minds on just a little curiosity driven blog!

    Well done my friend!

  149. Ferdinand Engelbeen (14:19:36) : David, the increase of d13C from the last glacial maximum to the start of the Holocene in the atmosphere was about 0.4 per mil, with CO2 increasing from about 180 to 260 ppmv.

    Golly. We were all the way down to 180? That’s the point where C3 plants start to gasp for breath… I guess that explains the grasses (C4) starting to dominate as they could still breath at those drastically low levels.

    The plants will scrub to the ‘gasping’ level in just a few years if we let them:

    http://chiefio.wordpress.com/2009/06/02/of-trees-volcanos-and-pond-scum/

    Raises an interesting point, though. It looks like part of the Ice Age profile is a near death experience for plants as they scrub the air to starvation levels of CO2. Better hope those volcanoes keep cranking it out, or we are headed for: 1) Ice Age. 2) Starvation from plants not growing. 3) Desert conditions as the cold does not evaporate as much water for rain.

    (It’s pretty well attested that there are far more desert areas during ice epochs of glaciation.)

    BTW, at least one researcher claims that the U and Th depletion ought to take about 4ish billion years to run low enough for vulcanism to drop off… or right about now… I sure hope he’s wrong. When the volcanos die, we die. From CO2 depletion.


    Not only is the change in d13C far larger than ever seen in the past, but completely opposite in trend (but in ratio to CO2 emissions…) compared to CO2 increases during glacial-interglacial transitions.

    Um, need I point out that we’re not in a glacial-interglacial transition? We’re in an interglacial-glacial transition. “I think this matters”.

    The start of the Holocene was warmer than the Roman Optimum.
    The Roman Optimum was warmer than the MWP.
    The MWP was warmer than now.

    The peaks are all getting lower. (I’ve left a couple out, but the trend holds).

    See how the ‘recent’ 10,000 years lines all decline in this graph:

    We’ve had our interglacial. It’s over.

    Yeah, it’s a geology thing, so it will take a few thousands of years to really notice, but hey, not my problem. The ice is returning. (Growth is shown in Antarctica. The North Pole is going to catch up next – being more ocean influenced it takes more time to get going – though the record shows that at the start of the Holocene it was free of ice in summers; so we’ve already got some ice back. Cheering for Summer Ice Cap at the north pole is, er, um, “not good”… it’s the essential step to the plunge into the glacial…)

    To put it in perspective, see this graph:

    Again, notice the ‘recent’ period is in decline. Then notice that our ‘interglacial’ width (while it didn’t start with as high a peak as the last one on the far right) is about as wide. We’ve had our shot and it’s all down hill from here.

    It’s just that it’s measured in thousands of years and you can walk further in one afternoon than the ice on average advances in a year. So we don’t notice. Toss in some ‘few hundred’ year ripple and it’s hard to even detect if you look for it (though the Vikings in Greenland detected it, and the ripple…)

    More and more graphs at:

    http://chiefio.wordpress.com/2009/10/09/how-long-is-a-long-temperature-history/

    Though I think this one:

    ought to be printed out an put on everyones walls with a “You Are Here” sticky on the far right, and “headed there” with a down arrow to the more stable state of darned cold. (Note also that PRIOR interglacial peaks are all higher than our present peak. Don’t know what dampened it, but it HAS been warmer before. A lot warmer. And warmer is not stable and is not a runaway ‘tipping point’. Colder is stable, and the only tipping point is to the downside. (The good news it that it takes 10,000 years to ‘be an issue’. The bad news is that the 10,000 years started a few thousand years ago…)

    So please ask yourself what happens at the EXIT from an interglacial, not the entrance. We are no where near the entrance…


    d13C levels in lake sediments and speleotherms are locally influenced, and can’t be used for global estimates.

    EVERYTHING is ‘locally influenced’. Just like the ocean “gut rocks” some fish poop out. What’s the c12/c13 ratio in them? Has it changed over time? Does the population of fish change over the glacial, and with it the gut rocks? The algae? Given that “gut rocks” were just recently discovered as ‘an issue’ I’m not willing to assert we have ‘perfect knowledge’ about them… or much else for that matter.

    The simple fact is that “we don’t know”. Trying to put lipstick on this pig and claiming we know things we don’t, so the only possible reason is fossil fuel burning is just silly. It’s broken logic.

    You can’t take a string of things we don’t really know and use them to prove a negative (that nothing else can do it) and then conclude a positive (so we must be the cause).

    So please take a while to admire what we don’t know while you are admiring all the things you think you know. Then admire where we are in time.

  150. “”” Sjoerd Schreuder (14:10:02) :

    “George E. Smith (13:19:13) : “””

    Sjoerd, I just reread your post in detail without all the cacaphony going on around my office; about the LCAO theory; and it sounds as if these molecules and their electrons act a lot more like blobs of mush, than little balls and springs snapped together on the desk. I’m quite impressed with the notion that the electrons spread over all three atoms; to render the two oxygens indistinguishable.

    Well I always thought that Atomic spectrocopy was the cat’s meow; but it seems that Molecular is even moreso.

    Thanks for taking the time with this; and you too Scott.

  151. “”” Sjoerd Schreuder (16:22:55) :

    George E. Smith (15:11:41) :

    Apologies if I went overboard with my explanation. It has been a long time since I studied theoretical chemistry but I still like the subject. As a result, I might have become a bit too enthousiastic. (And I’m a bit surprised the mods let it all through – this will be my last on this subject) “””

    Well Sjoerd; I don’t think the mods ever squelch anything because it is too accurate. Even if any post only registers with a single person; that is a useful communication; and I’ll be very surprised if I am the only one who gained any insight from the Posts that You and Scott made on this point.

    My formal education goes so far back into history, I’m almost embarrassed to describe some of the stuff I learned. My very first text book on Electronics; was the very famous 1938 “Admiralty Handbook of Wireless Telegraphy.” One of the things I learned from that, was that Copper was a plum pudding with 63 Protons in it, and 34 raisins embedded into the surface of the pudding, and 29 electrons whirling around the pudding to keep it electrically neutral. I think it was published just before the Neutron was discovered.
    Every day I use my State Secret Optical Design text book that was someone’s lecture notes in 1926. It used to be that if you showed up for an OSA convention and you didn’t admit to owning that text; you were considered a total imbecile.

    In any case the proddings that I found in both yours and Scott’s comments will help me direct my delving into the newer Chemistry texts I have been picking up from the Stanford University Book Shop. My entire collection of High school and University texts all vanished mysteriously off a ship somewhere in the Pacific Ocean 49 years ago last month, in 1961.

    So nothing you wrote was a waste of time; it is much appreciated.

    George

  152. As I understand it, the difference between c13 and c12 and c14 has to do with kinetics, as a function of resonant frequencies. (overly simplified). It can actually change or weaken reactions away from the individual atom, and heavier isotopes actually require more energy to split apart, and produce more energy upon combination.

    This is massively overly simplified, but the effect increases as mass of the initial ‘stable’ isotope decreases. I.e. hydrogen would double or treble the initial mass with extra neutrons (deuterium or tritium, respectively).

    Beyond that, I’ve no idea. Had the same question a month ago, regarding seafloor methane clathrates, carbon dioxide isotope composition in volcanoes, and isotopic composition of fossil fuels. That’s what came up in most of the answers. A great deal of the focus upon anthropogenic influence is focused on the change in carbon 13 ratios in plant uptake.

  153. Ferdinand Engelbeen (12:31:50) : Your argument presumes the Vostok ice core paleo-CO2 levels are absolutely correct. However, Beck found over 16,000 contemporaneous chemical CO2 measurements to be considerably higher than the Vostok data:

    http://docs.google.com/viewer?a=v&q=cache:W8qAaqX_oGgJ:www.friendsofscience.org/assets/files/documents/CO2%2520Gas%2520Analysis-Ernst-Georg%2520Beck.pdf+beck+co2+chemical&hl=en&gl=us&pid=bl&srcid=ADGEESjcGqq7FVuFAskjIVglwWIGLwmYFXujgkcpGvStUHBk_hfgNavi4T_uWw8FSUgjDX51cFB_L2PWVUyLkvWRwRLMJ01BUn6o6Pgbk4qcTmeXgsfcv09QrrCPwxRIzZmloglghZm0&sig=AHIEtbSV6hYRvyB03YogfpoV-eknbrvOMg

    In addition, Jaworowski has numerous arguments as to why the Vostok levels are questionable:

    http://www.co2web.info/np-m-119.pdf

    And so does JJ Drake:

    http://hockeyschtick.blogspot.com/2010/01/other-hockey-stick-co2-levels-part-2.html

  154. kadaka (12:47:49) :

    “Well, first was E.M. Smith’s great article on why detecting an anthropogenic CO2 signature based on atmospheric C12/C13 ratios is bunk.

    Now I have found Dr. Roy Spencer’s article right here on WUWT that lays out about the same.

    BOTTOM LINE: If the C13/C12 relationship during NATURAL inter-annual variability is the same as that found for the trends, how can people claim that the trend signal is MANMADE??

    So I am now up to two trusted sources which tell me that anyone telling me they can find a definite man-made CO2 signature and exact atmospheric amounts based on C12/C13 ratios, is not speaking out of the normal orifice used for transmitting verbal information.”

    You can add to that information the fact that the CO2 is measured at Mauna Loa an active volcano the many contribute to the “raw” CO2 measurements.

    http://volcanoes.usgs.gov/hvo/activity/maunaloastatus.php

    According to Dr Spencer “…There are quality control procedures applied later to exclude data when the wind is coming from the volcano crater above….” http://www.drroyspencer.com/global-warming-background-articles/carbon-dioxide-growth-rate-at-mauna-loa/

    I was a QC Engineer and Lab Manager for thirty years so I have a lot less “faith” in those quality control procedures than Dr Spencer does. Of course that is because of the number of lab techs I have had to fire for falsifying data. The great quality control found in Anthony’s surface station survey has done nothing to change my opinion…

  155. enneagram (14:47:10) :

    Gail Combs (14:17:48) :Sure beats starving people and animals because CO2 is limiting plant growth
    But it is precisely that what Al Baby wants, to limit the number of births among those smelly and working commoners and make possible the chosen ones only to survive, those brilliant minds as He himself, the supreme green kool-aid drinker.

    Yes that is why the USDA helped fund Epicyte’s Spermicidal Corn research. The !@#% stuff is now based here in North Carolina.

    “…Scientists have created the ultimate GM crop: contraceptive
    corn. Waiving fields of maize may one day save the world
    from overpopulation.

    The pregnancy prevention plants are the handiwork of the San
    Diego biotechnology company Epicyte, where researchers have
    discovered a rare class of human antibodies that attack
    sperm.

    By isolating the genes that regulate the manufacture of
    these antibodies, and by putting them in corn plants, the
    company has created tiny horticultural factories that make
    contraceptives.

    ‘We have a hothouse filled with corn plants that make
    anti-sperm antibodies,’ said Epicyte president Mitch Hein.

    ….Contraceptive corn is based on research on the rare
    condition, immune infertility, in which a woman makes
    antibodies that attack sperm….”
    http://www.ngin.org.uk/

    For more information: http://www.law.cornell.edu/uscode/17/107.shtml

    And just to make you really worry GMO corn was banned in Mexico however that did not prevent the spread of GMO genes

    “Contamination of Mexico’s
    corn by genetically modified (GM) varieties, including the banned
    StarLink, is much more widespread than previously reported,
    according to a new study sponsored by a coalition of indigenous and
    farmer groups.

    “Now we see that the contamination has spread at least to the
    south, central and northern regions of the country,”….

    http://www.encyclopedia.com/doc/1P1-85760970.html

    The idiots that came up with this and funded it should be on trial for “crimes against humanity” not us skeptics.

  156. Luboš Motl (08:01:08) :

    “Haha, I love the article and the picture of the two CO2 molecules.”

    So we can tell which one has charm, but I’ve never heard of sad quarks. :-)

  157. In the reader poll, I chose “Natural CO2 is less damaging than man made CO2″. As a chemist, I know there is absolutely no difference between the two molecules, but I had to choose that choice. It was calling out to me. — sorry

    (I feel better now).

  158. For the life of me I don’t understand why we trust that the CO2 measurement from Mauna Lao which is an active volcano and is near Kilauea another active volcano that has been erupting for years are accurate for the entire globe.

  159. George E Smith and C=O=C vs C=O-C:

    When diagramming a molecule, one shows how many bonds, not the 3D appearance of the bonds when looking from a particular angle. This is for two reasons: the number of bonds is useful information, and the 3D appearance cannot be drawn in such text sketches anyway.

    Therefore: C=O=C

    and BTW, looking at the molecule from 45 degrees, you would see both bonds in both places anyway.

    and BBTW: bearing quantum effects in mind, the ‘appearance’ of the molecule is at least partly undefined. :-)

  160. E.M.Smith (16:43:46) :

    Golly. We were all the way down to 180? That’s the point where C3 plants start to gasp for breath… I guess that explains the grasses (C4) starting to dominate as they could still breath at those drastically low levels.

    Not exactly, 180 ppmv is what was globally in the atmosphere, but that doesn’t mean that CO2 levels near the leaves were that low. In general, the CO2 levels over land near ground are a lot higher, due to soil respiration and organics decay (reason why I use mulching in my own garden). Only trees may have a more difficult time… But indeed, the start of C4 plants may be a reaction on lowering CO2 levels.

    Based on the multiple ice cores, it is clear that the CO2 levels are in a temperature controlled dynamic equilibrium (CO2 lagging temperature). Whatever the individual changes in vegetation growth/decline, ice caps covering land and ocean temperatures, there is a quite linear relationship between temperature and CO2 levels (pre-industrial anyway).

    I have no problems with the temperature/d18O profile of the glacials/interglacials, that is not where I object to your stories. Where I object is the d13C profile: that goes up with increasing CO2 levels in the pre-industrial past, and goes down nowadays. Thus in this period we see that the decrease in d13C is not by natural causes, neither is the increase in CO2, as temperature didn’t add more than 8 ppmv, if we may compare that to the past 420,000 (nowadays 800,000) years.

    EVERYTHING is ‘locally influenced’. Just like the ocean “gut rocks” some fish poop out. What’s the c12/c13 ratio in them? Has it changed over time? Does the population of fish change over the glacial, and with it the gut rocks? The algae? Given that “gut rocks” were just recently discovered as ‘an issue’ I’m not willing to assert we have ‘perfect knowledge’ about them… or much else for that matter.

    The simple fact is that “we don’t know”. Trying to put lipstick on this pig and claiming we know things we don’t, so the only possible reason is fossil fuel burning is just silly. It’s broken logic.

    You can’t take a string of things we don’t really know and use them to prove a negative (that nothing else can do it) and then conclude a positive (so we must be the cause).

    So please take a while to admire what we don’t know while you are admiring all the things you think you know. Then admire where we are in time.

    Some places are completely unsuitable for “global” measurements, other are better. Lake sediments are unsuitable, as these give the local d13C changes, influenced by local plant growth and decay and runoff. The same for speleotherms. The same for organic ocean sediments.

    Where to measure? The CO2 in ice cores shows CO2 levels and isotopic compositions of 95% of the atmosphere since at least a million years, far away from local influences. But smoothed (more over time). And coralline sponges show the broadly regional isotopic composition of seawater, which is influenced by local production, but that varies only slightly (+/- 0.1 per mil) over hundreds to thousands of years. Both ice core air samples and coralline sponges’ ocean samples show a huge decline in d13C (-1.4 per mil), far above the noise, completely in ratio with fossil fuel burning.

    Thus we don’t know all the details of all the processes involved, but we do know with huge certainty that the current CO2 increase and d13C decline are not caused by any known natural source (which should follow fossil fuel burning releases at such an exact ratio).

  161. @R. de Haan (08:07:39) :

    Even if we would cancel all air traffic for an entire year it would only reduce the the CO2 emissions by a meager 1.5 %. costing the economy billions of dollars a day.

    Air transport is a real soft spot of our economy and security.

    Without it we are back into the Stone Age!

    – – – – – – –

    That’s exactly where we are headed if the warmists and the hysterical Greenies get their way. Better check the tire inflation on your bicycles folks, only a hand pump will do.

  162. Hockey Schtick (17:37:02) :

    In short:

    – Beck’s data are broadly correct, but the problem is often taken at the wrong places: near huge sources. If one only uses historical data taken on board of ships or from the shore (with seaside wind), then ice core measurements are within the (wide) margin of the historical measurements. See further:

    http://www.ferdinand-engelbeen.be/klimaat/beck_data.html

    – Forget Jaworowski. His objections are completely outdated by the work of Etheridge (1996!) on three ice cores drilled at Law Dome (Antarctica). See further:

    http://www.ferdinand-engelbeen.be/klimaat/jaworowski.html

    – Forget JJ Drake. He makes a typical error of the type:
    A (temperature) causes B (CO2 levels), with a good correlation and
    A (temperature) causes C (ice age – gas age lag) with a good correlation
    which results in also a good correlation between B and C. Thus C influences B (or the opposite), according to Drake.

    That there is a good correlation between B and C is the result of A, but there is not the slightest causation between B and C and any “correction” based on that correlation has not the slightest physical meaning.

  163. Gail Combs (17:53:18) :

    You can add to that information the fact that the CO2 is measured at Mauna Loa an active volcano the many contribute to the “raw” CO2 measurements.

    http://volcanoes.usgs.gov/hvo/activity/maunaloastatus.php

    According to Dr Spencer “…There are quality control procedures applied later to exclude data when the wind is coming from the volcano crater above….” http://www.drroyspencer.com/global-warming-background-articles/carbon-dioxide-growth-rate-at-mauna-loa/

    The influence of local volcanic vents is limited (+4 ppmv), as is the influence of upwind conditions (depleted by valley vegetation -4 ppmv). These values are flagged and not used for daily to yearly averages. But including or excluding the outliers doesn’t change the yearly average or trend with more than 0.1 ppmv. CO2 is measured at a lot of places, including the South Pole (no volcano, no vegetation). All show similar averages and trends within a few ppmv. See:

    http://www.esrl.noaa.gov/gmd/ccgg/iadv/

    The rigorous calibration and quality control procedures for Mauna Loa (and other stations) is described here:

    http://www.esrl.noaa.gov/gmd/ccgg/about/co2_measurements.html

    I have a little more faith in CO2 measurements than in temperature measurements, as the first are based on far better and independent controls, involving lots of people from different organisations and laboratories…

  164. Steven Goddard said: “They (informationisbeuatiful.com) are trying to save face, but the 300,000 tons from the volcano probably exceeds the savings from grounded planes”.

    Steven, Are you not guilty of gross cherry picking here – of the sort that “AGW dismissers” tend to accuse the “AGW fearers”. The 300,000 tonnes figure from Patrick Allard is not based on measurements from Eyjafjallajoekull, but merely an “upper limit” for such an eruption. Likewise the 150,000 tonnes figure, which originates with Colin MacPherson(?) from Durham Univ is taken from data from a previous eruption nearby, so he is using the earlier eruption as a model for Eyja f.j. Yes, a model…, and we on WUWT all know the problems with “models” . I would humbly suggest that we should be using the figure of 15,000 tonnes provided by Icelandic vulcanoligists actually making measurements on Eyja f.j., since direct observation should, as we all recognise, be given greater credence than deductions from models.

    All the figures here and the references for them are taken from the informationis beautiful website that you quote.

  165. George Turner 08:41:19
    Disregarding all the high fliers, I love your extra oxygen point, something no-one else seems to have picked up on, but Howarth et al, I hear the theme tune from MASH running through my head ;-)

  166. Hmm, Icelandic banks go bankrupt, then the country is set fire to.
    It’s all an insurance fraud I tell you!

  167. Bill Hartree (02:16:12) :

    Your post makes it appear that you are commenting without having actually read my article above. I will post it for you again.

    Volcano CO2 budget (CO2 is emitted independent of ash)
    ~200,000 tons per day X 30 days of eruption = 6,000,000 tons of CO2.

    Plane CO2 Budget – assumes half of EU planes haven’t flown for the past six days
    340,000 EU tons per day X 0.5 EU shutdown X 6 days = ~1,000,000 tons of savings.

    People using alternative transportation (as Anthony and the BBC pointed out) as a replacement for aircraft – cars, trains, battleships , etc. = ~1,000,000 tons of extra CO2
    Is a battleship more “green” than a jumbo jet?

    The total gain is 6,000,000 – 1,000,000 + 1,000,000 = 6,000,000 tons of excess CO2 from the volcano. The temporary aircraft shutdown has little or no net impact on CO2 emissions, but the volcano has a large impact.

  168. @kadaka (09:55:15) :

    Yes, very interesting article. It further highlights that we’re just now starting to figure out the “unknown unknowns”, to mis-quote Donald Rumsfeld.

  169. I had an article of Moonbat’s sneak up on me while reading the Sydney Morning Herald today. I shall read that journal no more, just in case it happens again.

    He is telling us that the current level of aviation traffic is ‘unsustainable’. Tell Al Baby, and see if he’ll stop…..

  170. Bernd Felsche (19:20:46) :

    Luboš Motl (08:01:08) :

    “Haha, I love the article and the picture of the two CO2 molecules.”

    So we can tell which one has charm, but I’ve never heard of sad quarks. :-)

    Hmmm …… that’s Strange ….

  171. George E. Smith (17:06:32):

    &

    George E. Smith (16:43:50) :

    Thanks for the comments, I’m glad we were able to help out. I, too, learn a lot in areas outside my expertise when reading the comments on this site, so I was glad to contribute some chemical knowledge.

    On a topic related to CO2, can someone point me to a link where the radiative forcing factor for CO2 was derived? I’ve never run the numbers myself, but I have an idea on why it may be overestimated, so I wanted to check it out.

    Thanks,

    -Scott

  172. Steven Goddard wrote: “Your post makes it appear that you are commenting without having actually read my article above”.

    Steven, I was actually quoting not from your original posting but from a subsequent comment by you on the comments section, where you actually upped your original estimate of daily CO2 production from ~200,000 to 300,000 tonnes per day. I did actually read your article, which is how I got to know about the informationisbeautiful website: many thanks for introducing me to it!. My original point was to question your decision to go with a figure in the region of 150,000 to 300,000, based on “model data” from an eruption from a different volcano, rather than the 15,000 tonnes per day actually measured by vulcanologists from Eyja f.j. over the course of the last few days. I had assumed that you would have done as I did and investigated informationisbeautiful’s sources of information (for which they provide comprehensive links) for the 15,000, 150,000 and 300,000 figures, but in case you haven’t then you should be able to understand my comment better if you do so.

    As for your claim that any reduction in emissions from planes would have been largely offset by emissions from cars, trains, buses and ships you may be right: I don’t feel I have the knowledge to comment either way on this.

  173. Volcanic CO2 has a lower proportion of C14 than man made CO2.

    I doubt that it makes any significant difference, certainly none that is measurable.

  174. Gail Combs (18:33:07) :

    ‘We have a hothouse filled with corn plants that make
    anti-sperm antibodies,’ said Epicyte president Mitch Hein.

    Gail, I don’t know exactly what Epicyte’s anitbodies are, but as a result of normal digestive mechanisms, antibodies [a form of protein] are not absorbed intact into the human body intact, except for a brief period in neonates when [some?] antibodies in breast milk colostrum are absorbed intact:

    http://www.vivo.colostate.edu/hbooks/pathphys/digestion/smallgut/absorb_aacids.html

    Apparently only very short chain peptides, up to tripeptides = three aminoacids in chain – total, make it in.

  175. I wrote this letter to Dr. Ball, who had an excellent article in Canada Free Press:

    Dr. Ball:

    I enjoyed your article very much.

    As a physical organic chemist of 40+ years, and an expert on liquid and vapor diffusion through solids and semi-solids, I have to comment about ice core CO2.
    I will be very brief.

    CO2 diffuses through solid ice. The diffusion coefficient, very slow, but relevant to geologic time, was determined 2 years ago at Scripps Oceanographic. The diffusion depends on the diffusion coefficient, temperature, and time, but it directly depends upon INITIAL CONCENTRATION according to Ficks’ first and second laws of diffusion. The diffusion proceeds, in a concentration dependent manner, dc/dt, until equilibrium is reached. According to these laws, diffusion will proceed until the outside concentration is approached asymptotically.

    So, all ice core CO2, given enough time, will reach the same level! SO, the old cores will lose CO2 more, and faster yet if the concentration is high in the old core.

    So the number assumed, of ice cores being 20% low, is a completely wrong supposition. If CO2 were very high in the past (had to be very high for dinosaurs to get so large, commensurate with the fast rate of plant growth in response to CO2), the CO2 would have been lost to our contemporary measurement. Has to be. It’s physics!

    However, working backwards from Fick’s Second Law, if we know the age of the sample, and the current measurement of CO2, and assume a number for an average outside concentration, we can extrapolate, using a simple differential equation, to find the initial concentration now that we know the diffusion coefficient.

    Bob Gyurik
    Sanibel, FL

  176. “”” Ron House (23:20:35) :

    George E Smith and C=O=C vs C=O-C:

    When diagramming a molecule, one shows how many bonds, not the 3D appearance of the bonds when looking from a particular angle. “””

    Ron, of course I am; and always have been; well at least as far back as about 1950, aware that CO2 contains two double bonds and is a linear molecule, and that it was coventionally represented by O=C=O just as Steve has ita t the top of this thread; except in 1950, they did not have smiley faces on molecules. I believe I am also correct in saying that in 1950 I was certainly NOT aware, that H2O was bent at that all important 104.5 or so degrees; I’ve only been aware of that for less than half that time.

    My O=C-O was a whimsical attempt to use the limitations of my keyboard to create what I thought was a reasonable 3-D “model” of a CO2 molecule, in which the right hand bond pair was viewed edge on. It was never intended to be a full quantum chromodynamics thesis on the structure of CO2; assuming anybody would ever bother to construct such an edifice.
    The only “four bond” plastic atoms I have at my desk, are various colors of balls with tetrahedrally located holes, into which I can insert bendable plastic “links” to build “artist’s impression” models of the Zinc-Blende and Wuzite Crystal lattices of the common III-V compounds. I could also build the Diamond lattice for Carbon, Silicon or Germanium if I wanted to just build a zinc-Blende lattice with a single color balls. There is no elemental equivalent to the binary Wurzite lattice.
    The Arsenides, Antimonides, and Phosphides of Boron, Aluminium, Gallium, and Indium, are all Zinc-Blende lattices; whereas the Nitrides of Aluminium Gallium, and Indium are all Wurzite lattices. Then of course there is Boron Nitride; the odd-ball, which can have either the Zinc-Blende lattice (Borazon) but usually has the BN lattice which is a lot like Graphite with hexagonal cellular layers; but the adjacent BN layers are displaced from the Graphite layers.

    But if I use my plastic ball and rod pieces to make CO2, then I get the two bond pairs to the Oxygens at right angles to each other about the linear molecule axis. And the whole reason for trying to depict this structural form was to explain the two degenerate bending modes of the CO2 15 micron absorption as depicted in this animation:

    http://science.widener.edu/svb/ftir/ir_co2.html

    In those animations of the bending modes, it is assumed that the oxygen can move out of the plane containing the pair of bent spring bonds; but that the other oxygen would have to move out of a perpendicular plane containing its two bonds, giving the up-down, and side to side vibrations seen in the animations.
    I presume that since the pair of bonds to the Oxygen can stretch as in either the symmetrical or assymmetrical stretch modes, that it is also possible to have one of the pair of Oxygen bods stretch while its companion shrinks, so that the O can warp sideways in the same plane of the two bonds; but this presumably would be a higher frequency mode of vibration than the 15 micron bend.

    And as has been explained in detail by Scott, and Sjoerd, the reality is a lot more complicated than I can construct with my plastic balls, and flexible rods.

    I’m familiar with the fact that organic chemists draw Benzene rings with alternating double and single carbon bonds around the ring; but that apparently that pattern isn’t static; so evidently one of those electrons can jump over a carbon into the adjacent CC space thereby moving the single and double bonds around dynamically. So how can you show that on a simple pictorial sketch; let alone try typing it on a keyboard.

    Well this is all very interesting; but not too useful in deciding whether we are on our way to a CO2 tipping point; or whether the CO2 comes from a C3 breathing plant or a C4, or maybe from some trilobite’s remains; or an Arabian oil well.

    I’m actually only casually interested in the origins of the carbon or whether it is man made or not; to me that is largely inconsequential; because I don’t believe that the CO2 Greenhouse effect (which I fully admit to) has any appreciable impact on global temperatures; compared to the total feedback control exerted by the bent H2O molecules; which alone, exists in earth’s atmosphere in all three phases of normal matter. Besides humans emit more H2O to the atmosphere than they do CO2; so we are guarding an empty hen house.

  177. “”” bubbagyro (10:34:26) :

    I wrote this letter to Dr. Ball, who had an excellent article in Canada Free Press:

    Dr. Ball:

    I enjoyed your article very much. “””

    So Bob, I’m interested in the essence of your letter to Dr Ball.

    First off, you say that Scripps determined the CO2 diffusion coefficient (presumably in ice) two years ago. I wonder if Dr Steve Piper had a hand in that. He’s a CO2 expert at Scripps; whom I know only though some fly fishing e-versations; and he has been kind enough to send me various papers on CO2.

    Do you know if Scripps was able to determine any temperature coefficient of the diffusion coefficient.

    But now, if I understand your above letter; you seem to be saying that the diffusion rate depends on the “initial” CO2 amount in the sample. Is this similar to the diffusion of impurities into say silicon, in the fabrication of semiconductor devices. In that technology we have several processes for getting some “lump” of impurity material (B or P say) into the Si; including Ion implantation; but then subsequent heat treatments will redistribute the “lump”, and in that case, the diffusion process does depend on the amount of impurity and its peak concentration in the original lump.

    With the CO2 in ice thing; don’t they have a problem, that the distance from the “sample” to the ambient (atmosphere) must be largely unknown; unless they rely on the ice layers that presumably are laid down annually; but if the atmospheric CO2 is varying substantially over time, then it would seem they have a very complex deposition structure to subject to diffusion calculations.

    Well maybe it is just a matter of how much supercomputer power you have access to.

    Maybe you can comment on a related issue. The annual cyclic variation of atmospheric CO2 in the arctic; covering pretty much the entire arctic ocean to the pole, and maybe some of the surrounding land, has a peak to peak CO2 variation of aboput 18 ppm; which is three times the Mauna Loa amplitude.

    Now I have postulated, that a possible cause or at least a contributor to this could be the melting and regrowth of the arctic sea ice. Assuming that the ocean surface water, must contain a lot of CO2 per Henry’s law, and the water being sub zero; upon freezing, it seems that CO2 along with the salt, must be excluded from the growing solid via some “segregation coefficient”. If the water CO2 content was near the equilibrium (saturation) value set by Henry’s law, then the addition of a considerable amount of CO2 that is being excluded from the growing ice, might then result in a lot of that CO2 escaping from the water into the atmosphere to comply with Henry’s law limits.

    Now Dr Piper was not too moved by my postulate; and suggested that perhaps I needed reprogramming.

    So perhaps Bob; you can enlighten us as to how much CO2 would be incorporated into the growing sea ice from the water; versus the amount that would remain behind in the water. The ice evidently is high purity fresh water, aside from brine inclusions in voids; so I wonder just what redistribution of the CO2 in the water as it freezes, would be expected to take place.

    Don’t want to burden you with any chores; but if some of this is at your fingertips; it would be much appreciated to learn what happens.

    George

  178. E.M.Smith (14:51:55) :
    And for all the folks talking about plants having preferential absorption of different isotopes remember that C3 vs C4 plants have different enzyme systems and thus different ratios. So you also get to figure out the historic ratio of these two plant metabolism types. For bonus points you get to figure out how both have evolved over time AND how both work in a differential way at different concentrations of CO2 and with different atmospheric ratios of C12, C13 and even C14 just for fun…

    Ferdinand Engelbeen (00:53:48) :

    Sorry I didn’t respond sooner, I was planting my victory garden! Ferdinand, I’m inclined to believe that we must agree to disagree. I’m entirely unconvinced that CO2 discrimination is measuring human interference through fossil fuel use with sufficient precision, especially within the short time-frame available. In addition to E.M. Smith’s contributions, there are two many confounding effects, some examples following.

    For example, irradiance influences the isotopic ratio for marine algae. So have there been any studies relating tropical cloud cover to isotopic discrimination?

    Abstract
    The ratio of l*C : 13C was measured for Emiliania huxleyi cells grown under a range of irradiances in batch culture. Based on the assumption that HCO was the carbon source, the maximum discrimination against 13C in the decalcified E. huxleyi cells was 24.6?& at 4.8 mol photons m-* d-l and the minimum discrimination was 17.9?& at 0.5 mol photons m-* d-l. In calcified cells, the range of 13C isotope discrimination was
    markedly lower (12-217~). In both calcified and decalcified cells, the carbon isotopic composition of and carbon isotopic discrimination by E. huxleyi was a significant linear function of irradiance from 0.5 to 4.8
    mol photons m-* d- I. The relationship between isotopic discrimination and irradiance in E. huxleyi provides new evidence that the 13C of the oceanic POC samples should not be treated simply as a function of sea
    surface temperature or [CO,],,. We propose that the P3C of E. huxleyi was controlled by irradiance through variation in the intracellular HC03- -derived CO2 supply which influenced the discrimination of ribulose
    1,5-bisphosphate carboxylase/oxygenase (rubisco) against 13C.
    The ability of the ocean to buffer the concentration of CO2 in the atmosphere through the so-called biological pump depends on the extent to which the photosynthetic rate of marine phytoplankton is limited by the concentration of CO2 in the water. If CO2 becomes available to phytoplankton by passive diffusion through the boundary layer around the cell, then the growth of large cells, which are believed to contribute disproportionately to the biological pump, could be limited by CO2 availability. However, many species appear to have the ability to circumvent diffusion control through the use of carbon-concentrating mechanisms (CCMs) such as active CO2 uptake, bicarbonate (HCO3-) transport, and carbonic anhydrase activity. These mechanisms are likely adaptations to the fact that the main carbon fixing enzyme, ribulose-1,5-bisphosphate carboxylase-oxygenase (Rubisco), is less than half saturated at normal seawater CO2 concentrations.

    And the tiny fraction that man is producing has little affect on biological activity, the mole ratio figures are in dispute.

    Isotopic disequilibrium experiments were also performed in the field to estimate the extent of photosynthetic bicarbonate (HCO3-) uptake in the oceans. The experiments were conducted in the Southern Ocean during the Southern Ocean Iron Experiment (SOFeX). In contrast to the results with P. tricornutum, approximately half of the photosynthetic inorganic carbon uptake was direct HCO3- uptake, the other half being direct CO2 uptake (passive and/or active uptake). A low-CO2 treatment induced an increase in uptake of CO2 through increased enzymatically mediated extracellular dehydration of HCO3- (carbonic anhydrase activity), which was at the expense of direct HCO3- transport across the plasmalemma. Because of the presence of CCMs, biological productivity in the Southern Ocean is unlikely to be directly regulated by natural or anthropogenic variations in atmospheric CO2 concentration. These results are consistent with stable isotope fractionation models and could have important implications for the global biogeochemical cycle of carbon.

    For brevity, here are just blurbs from the results from other studies:

    A review and experimental study of the various factors that influence CCM activity and therefore photosynthetic carbon isotope fractionation revealed that, other than CCMs, several factors that have been essentially ignored in the scientific literature may also contribute to the isotopic signature of photosynthetic organic matter. Isotopic fractionation during photosynthesis in P. tricornutum was found to be well correlated to changes in Rubisco enzyme kinetics. The contribution of carboxylases other than Rubisco to photosynthetic stable carbon isotope fractionation was also examined.

    A multitude of factors may influence overall photosynthetic carbon isotope fractionation. Understanding these factors will be crucial to the use of isotopic analyses for paleo-CO2 reconstruction.

    And, water deficiency (drought) affects the isotope discrimination, influencing terrestrial uptake and evolution:

    Arndt SK, Wanek W. Use of decreasing foliar carbon isotope discrimination during water limitation as a carbon tracer to study whole plant carbon allocation. Plant Cell Environ. 25: 609-616 (2002)

    Irradiance affects respiration isotope composition:

    Barbour MM, McDowell NG, Tcherkez G, Bickford CP, Hanson DT. A new measurement technique reveals rapid post-illumination changes in the carbon isotope composition of leaf-respired CO2. Plant Cell Environ. 30: 469-482 (2007).

    We know far less than we think we know.

  179. George:
    Yes, same as doping silicon. All gases diffuse into and through solids.

    Diffusion does depend on “d” the thickness of the substrate. However, molecules “don’t know” what is happening on the outside, no matter how thick the substrate. Fick’s 2nd law assumes that the molecule diffusing is novel – in other words, that there is no molecule in the substrate through which it is diffusing.

    The fact that the molecules “don’t know” means that the diffusion rate is proximal. For a substrate that already contains CO2, like the ice, then the diffusion depends upon ∂C, the immediate concentration difference. If, however, there is melting, or something “sucking molecules away” on the outside, then there will be a differential gradient that will affect the rate coming from the reservoir. The response time will depend upon the diffusion coefficient.

    There is one other factor. Pressure. There is a gradient of pressure that can hinder diffusion, countering Fickian first order diffusion. Under a glacier, then, diffusion will be hindered. However, when the core is removed, then diffusion will go unabated.

    Say, for example, during an ice age, CO2 and ice are laid down (CO2 is soluble in pure water at parts per hundred, so solubility is not a factor; the CO2 concentration of the atmosphere, then, is similar now to that trapped in the snow that has fallen, at say, a part per thousand), and the snow compacts into ice quickly (over tens or hundreds of years, not millennia). When the glacier melts, and pressure is reduced (again, hundreds of years), then the pressure within the bubbles in the core in question are under relatively high pressure.

    This is why I cannot compute using Fick’s law because there are too many unknowns, Would need a Cray.

    Yes, I believe it was Dr. Piper who did the Scripps work. If you know him, perhaps you could get his counsel on this.

  180. stevengoddard (09:15:44): “If you look at the IIB spreadsheet linked from their site”

    Steven, I find this sentence of your reply incomprehensible. What is “IIB”, and to whom does “their” refer?

    The entry on the “pre-eruption” emission of CO2 contains no attribution, unlike most of the other entries, so I have no way of assessing its reliability. Perhaps I could help you out here by providing a reference: it’s actually in one of the links provided by the informationisbeautiful article to which I’ve referred you, but here it is: http://www2.norvol.hi.is/Apps/WebObjects/HI.woa/swdocument/1015769/Gas+report+-+Eyjafjallaj%C3%B6kull+2010.pdf
    The data were gathered on 1st-2nd April, i.e. during the eruption and not “pre-eruption”. If you look at the bullet points towared the end of the article you will see that the emission of SO2 was 3000 tonnes per day and that the approximate molar ratio of CO2 to SO2 is 15:3. This actually means that the CO2 output would be more like 10,000 tonnes per day: informationisbeautiful’s figure was an over-estimate. Possibly, the author of the spreadsheet you cite, whose source remains a mystery to me, made the same mistake.

    So, there you have it: a measurement-based figure for CO2 output during the eruption. As I have explained to you in my two previous comments, your 150,000 tonnes per day figure is not based on any measurements of Eyafjallajoekull, but rather on the speculative assumption that the current Eyja f.j. eruption is emitting at the same rate as a previous eruption of another, unnamed Icelandic volcano.

    Would you care to comment?

    So there you have it

  181. bubbagyro (10:34:26) :

    CO2 diffuses through solid ice. The diffusion coefficient, very slow, but relevant to geologic time, was determined 2 years ago at Scripps Oceanographic. The diffusion depends on the diffusion coefficient, temperature, and time, but it directly depends upon INITIAL CONCENTRATION according to Ficks’ first and second laws of diffusion. The diffusion proceeds, in a concentration dependent manner, dc/dt, until equilibrium is reached. According to these laws, diffusion will proceed until the outside concentration is approached asymptotically.

    I think that I have read the article too (or were it Japanese tests I have read?). They measured the diffusion speed of ice at the same circumstances of the deep ice core of Vostok.
    If I remember well, they compared the high pressure and low temperature CO2 diffuse speed against ambient pressure. Quite a difference with the real circumstances, where there is no practical pressure difference between ice at 2000 m and 2001 m depth. The same point for CO2 levels: the diffusion speeds I do remember were so low that the CO2 partial pressure difference over a meter of ice is practically irrelevant as driving force. The more that CO2 levels did go up and down over time, thus diffusion at the top layers would have been two-ways.

    More important, even over 800,000 years of layers, the ratio between CO2 levels and temperature (proxy) didn’t change over time: for each glacial – interglacial transition, CO2 goes up and down with temperature (with a lag). If there was any (vertical) migration, the CO2 levels would be smeared out and the ratio would diminish with each transition 110,000 years further back in time.

    Further, none of the ice cores from Antarctica which are used show any remelt of layers (with a few exceptions), relaxation is done at -20 C for up to a year (by far not long enough for the migration of CO2) and measurements are done by cold grating under vacuum over a cold trap, effectively removing any CO2 from any liquid water at the ice core’s surface layer.

    Ice cores with very different circumstances of temperature, precipitation and salt/dust inclusions show the same CO2 levels at the same gas age for overlapping periods, the most recent high accumulation ones (Law Dome) have an overlap of 20 years with the South Pole atmospheric measurements.

    Last but not least, CO2 levels in ice cores are measured at 180-300 ppmv. Today we measure 390 ppmv in the atmosphere. Backcalculating would mean that CO2 levels in the past would have been even lower, if migration from the outside world to the inside ice core would have occured…

  182. Tim Clark (13:07:41) :

    Sorry I didn’t respond sooner, I was planting my victory garden! Ferdinand, I’m inclined to believe that we must agree to disagree. I’m entirely unconvinced that CO2 discrimination is measuring human interference through fossil fuel use with sufficient precision, especially within the short time-frame available. In addition to E.M. Smith’s contributions, there are two many confounding effects, some examples following.

    The examples you did give were about the d13C changes in organic carbon, which is not of interest here, as total biolife on earth (including animals and ocean creatures) produces more oxygen than it uses. That means that the bio world uses 12C and increases the 13C/12C ratio and that the bio world removes CO2 from the atmosphere. Thus the bioworld as a whole is not responsible for the increase of CO2 in the atmosphere, neither for the d13C decline we measure at least in the past 50+years.

    The (deep) oceans have a higher d13C ratio in CO2 than in the current atmosphere, even taking into account the (two-way) isotopic fractionation between water and air at the ocean’s surface. Thus oceans can’t be the cause of the increase of CO2 in the atmosphere, or we should see a d13C increase.

    d13C ratio’s from the ancient atmosphere are measured in ice core gas composition and doesn’t change with more than 0.4 per mil over glacial-interglacial transitions. When temperature and CO2 level goes up, d13C level goes up. Until some 150 years ago: CO2 goes up, but d13C level goes sharply down (in ratio with fossil fuel use) now already 1.4 per mil lower than during the whole Holocene.

    d13C ratio’s from the oceans are measured in coralline sponges, which is inorganic carbon built from (bi)carbonate, without changing the isotopic composition compared to the surrounding seawater (coccolith shells are similar at near zero per mil d13C). These also show little variation up to about 1850 (+/- 0.1 per mil) and a sharp decline thereafter. Again in ratio to fossil fuel use.

    Thus as neither biolife, nor the oceans are the source for the CO2 increase, neither of the d13C decline and both changes track fossil fuel use with an almost perfect fit, there is little doubt that humans are responsible for the increase of CO2 in the atmosphere.

    That doesn’t imply that the effect of the increase is disastrous, that is a complete separate discussion.

  183. Tim Clark (13:01:32) :
    I don’t think you meant biochemical and then inferred a physical chemist would know. You should ask someone who has had Enzymology; and actually it makes 2.03% difference from corn chloroplasts in one of the most quoted pioneering work (peer reviewed ;~P)

    Ferdinand Engelbeen (13:53:58) :
    The story doesn’t determine what caused the fractionation in the ultimate enzymic reactions (interesting that it is the bicarbonate ion which is mainly used). The first fractionation at the air-water boundary indeed is a matter of kinetics (the same happens at the air-ocean border in both directions), but as for many biochemical reactions size and 3D-structure is important, I still wonder if that also is the case for 13CO2 vs. 12CO2 incorporation.

    Ferdinand,
    These folks indicated it is a little of both, but weighted toward RUBISCO.

    Where ci is the intercellular leaf CO2 concentration; δ13Cair is about –8‰VPDB, a is the fractionation caused by the slower diffusion 13CO2 relative to 12CO2 (4.4‰), b is the fractionation caused by discrimination of RuBP carboxylase against 13CO2 (27‰) and ca is the atmospheric CO2
    concentration. Field observations of average diurnal ci values correlated with whole-leaf carbon isotope values support this relationship.

  184. Ferdinand:
    I do not think that the last paragraph is true. In accordance with the geologically slow diffusion rate, the recent CO2 levels, measured by different proxies, are very low. We are IMHO in a CO2 starved state compared to the dinosaur era, certainly, and maybe in the last couple hundred thousand years. The “back diffusion” conditions you mentioned would not have existed except for thousands year times. Not enough time, IMO, for the high CO2 content in the ice to have diffused out in equilibration with the very recent concentration.

    According to diffusion physics, any putative high CO2 concentrations in the past would be long lost to our measurement. We do know that high concentrations of CO2 did exist in the past, the question is when. We certainly could not see that by current methodologies.

  185. stevengoddard (09:15:44):

    Steven, After visiting informationisbeautiful I’ve worked out who “their” refers to in your message. You are taking the 15,000 tonnes figure as “pre-eruption” on the authority of … the informationisbeautiful website.

    So that particular question of mine is answered. If you could still comment on the rest of my posting of 14:05:32 I’d be most grateful.

  186. “”” bubbagyro (13:13:42) :

    George:
    Yes, same as doping silicon. All gases diffuse into and through solids. “””

    Thanks Bob; I have always thought of the simple diffusion as being akin to the “ballroom dancing” effect, in that the movement of individual “dancers” is influenced by where the holes are on the dance floor; so everybody steers towards the empty space; which of course thereupon moves to somewhere else. So local concentration gradients point to which direction is downhill, and the rolling stone heads in that direction at a rate that reflects the steepness of the hill.

    I was fortunate enough to get my early solid state Physics directly from Dr Andrew Grove, former President and co-founder of Intel; when we both were at Fairchild Semiconductor.
    In his classic text on the Physics and Technology of Semi-Conductor Devices Grove gives:- C(x,t) = Cs.erfc (x/2sqrt(Dt)) for the one dimensional diffusion in x and t (time), with Cs as the fixed surface (predep) concentration; yielding the compementary error function diffusion profile.

    This step is then followed by a so-called Drive in Diffusion where a regrown oxide blocks off the surface, trapping the fixed “clump” of dopant, which then redistributes in a Gaussian distribution, which gives:-
    C(x,t) = (Q/sqrt(piDt))exp (-x^2/4Dt) ; Q being the fixed quantity of impurity in the clump. The surface concentration constantly drops from the initial Cs level as the dopant progresses into the crystal.

    I believe that this analysis relies on an assumption that the dopant species, is in fact incorporated into the crystal lattice which results then in a local charge concentration as well since the dopants are not isoelectronic with the native crystal (silicon) species, so either make it (p) type (Boron) or (n) type (phosphorous). So I beleive there is both a concentration gradient driving force and also a Coulomb force due to the charged foreign species. If the impurities are interstitial, as they can be in in very high doping levels or in weird crystals like Gallium Arsenide, then the interstitial impurities diffuse under their own laws; which are more elaborate than the above.

    But all that is rather unrelated to CO2 diffusion through ice, since I don’t quite see any Coulomb component to the driving force, as the CO2 molecules are hardly likely to be incorporated into the ice lattice; well I think that’s the case anyway.

    Thanks for the insight; fancy that, Dr Steve may be the culprit. He seems like a very nice chap based on my exchanges with him. We are both avid salt water fly fisherfolk. I’ll have to bend his ear about the CO2/ice diffusion coefficient.

    He already told me that his primary CO2 interests; were NOT actually directed towards any climatic interests; although he indicated that some of his CO2 colleagues at Scripps were. Like I said Steve yanked my chain a bit, and said I needed reprogramming. But then I suspect that scripps is one institution where it is not fashionable to be bucking the party line. Wouldn’t mind working there though, since La Jolla, and San Diego, has much better fishing that San Francisco. Well you’ve got the best fishing right in your back yard; I have a great affinity for tarpon on the fly.

    George

  187. Hooked a tarpon last year on light tackle from the shoreline, using shrimp, but of course he snapped the line.

    Fairchild? I used Fairchild people in the 80s. I patented an electronic CMOS device for dosing medicine automatically for cattle in the 3rd world, so people would not have to round them up to dose once a month. The fellow who actually designed the chip to my specs, was the one who developed the deep channel CMOS chip for musical greeting cards. The rest of the solid state and mechanical components was built by a group called I2P.

  188. http://www.redorbit.com/news/science/1852153/volcano_co2_output_could_be_150300000_tons_daily/

    Volcano CO2 Output Could Be 150-300,000 Tons Daily

    Posted on: Tuesday, 20 April 2010, 06:40 CDT

    Experts said on Monday that the volcano in Iceland is emitting 150,000 to 300,000 tons of carbon dioxide (CO2) per day, a figure comparable to emissions released from a small industrial nation.

    The estimation is based on gas composition of an earlier eruption on a volcano adjacent to the Eyjafjallajokull volcano. If figures are correct, the CO2 released by this volcano would be “150,000 tons per day,” Colin Macpherson, an Earth scientist at Britain’s University of Durham, said in an email to the AFP news agency.

    Patrick Allard of the Paris Institute for Global Physics (IPGP) said the amount could be as high as 300,000 tons per day.

  189. Ferdinand Engelbeen: earlier you linked to your graph:

    how do you explain the divergence between the cumulative emissions exponential curve and the co2 level linear trend?

  190. “”” bubbagyro (16:57:20) :

    Hooked a tarpon last year on light tackle from the shoreline, using shrimp, but of course he snapped the line.

    Fairchild? I used Fairchild people in the 80s. I patented an electronic CMOS device for dosing medicine automatically for cattle in the 3rd world, so people would not have to round them up to dose once a month. The fellow who actually designed the chip to my specs, was the one who developed the deep channel CMOS chip for musical greeting cards. The rest of the solid state and mechanical components was built by a group called I2P. “””

    Interesting; I was hired into Fairchild by Dr Victor Grinich, who was the only EE amongst that founding fabulous eight, that included Robert Noyce and Gordon Moore; in mid 1967. He managed the Test Instrumentation division of the Company. Odd thing is that he later left Fairchild and was a principal investor and consultant to a company called Identronix (I think that is correct) that made implantable devices to put inside cows to keep track of them.
    Fairchild was actually out in front of most people in the MOS technology; I actually saw samples of some of their very early prototypes at Tektronix in about 1965-6. Problem was they had about four different R&D groups each working on a different MOS technology; p-channel, n-channel, 4-phase dynamic and some others. Instead of co-operating to figure out the most logical technology to proceed with, they all worked at pulling the rug out from under the other groups, to try and grab their R&D funds for themselves. The result was that Fairchild never did become a significant factor in MOS; Bob Noyce got frustrated with the whole thing, but was too nice to fire people; and his solution was to leave and found Intel, and then hire the good people there. I was also there during the great Hogan’s Heroes raid on Motorola; which also never panned out for Fairchild.

    But it certainly was a hive of some bloody smart people, in those early days; and it really was the true source of Silicon Valley. I left in 1970 to help found an early and mildly successful LED startup Company.

    But to me; the ultimate Irony, was when Bill Shockley at Shockley Transistor, looked at the proposed planar process for making a transistor; that John Hoerni, Moore and Noyce came up with; and then told them; “If you guys think that is the way to make transistors; why don’t you go and start your own company, and do it !” Well they took him up on it, and Fairchild Camera and Instrument Corp, decided to take the risk and fund them.
    That maybe the origin of the saying; “Some of MY best decisions, were made by somebody else !”

  191. Hockey Schtick (22:02:54) :

    how do you explain the divergence between the cumulative emissions exponential curve and the co2 level linear trend?

    The CO2 level is not linear either, but is going slower up than the emissions, with a rather fixed percentage of the emissions. If you plot the accumulated emissions vs. the accumulation in the atmosphere, it is a straight line:

    where the first halve of the accumulation is from ice cores and firn, the second halve from Mauna Loa for atmospheric measurements.

    The reaction of the CO2 cycle on disturbances mainly is by the oceans, which act quite linear on an increase in the atmosphere: if the CO2 (partial) pressure difference between atmosphere and oceans doubles, the uptake by the oceans doubles too, but that is only possible if the CO2 pressure in the atmosphere increases, as the CO2 pressure in the oceans only changes with a (relative) small amount with temperature.

  192. bubbagyro (15:39:48) :

    I do not think that the last paragraph is true. In accordance with the geologically slow diffusion rate, the recent CO2 levels, measured by different proxies, are very low. We are IMHO in a CO2 starved state compared to the dinosaur era, certainly, and maybe in the last couple hundred thousand years. The “back diffusion” conditions you mentioned would not have existed except for thousands year times. Not enough time, IMO, for the high CO2 content in the ice to have diffused out in equilibration with the very recent concentration.

    According to diffusion physics, any putative high CO2 concentrations in the past would be long lost to our measurement. We do know that high concentrations of CO2 did exist in the past, the question is when. We certainly could not see that by current methodologies.

    I agree that any “short” lived higher CO2 level of a few hundred years wouldn’t be measured in the oldest ice cores, because the resolution is too wide. But either a long period of slightly higher levels or a short period with very high levels would have been noticed. As each interglacial was some 10,000 years (or longer), and the glacials were 100,000 years, any noteworthy diffusion would have leveled off inside and outside CO2 concentrations and between the higher (280 ppmv) and lower (180 ppmv) CO2 concentration layers. Thus indeed, the CO2 levels over the last 800,000 years in average were much lower than we see nowadays (and in most of earth’s history).

    Diffusion always goes 2-ways (except if one uses reverse osmosis, but that is not at order here), but the net result is from the higher level to the lower level. Thus if we see lower levels in ice cores and there was (any) diffusion, that means that past levels were even lower in the atmosphere than measured in the ice core… But I don’t think that diffusion played any role at all.

  193. Ferdinand Engelbeen (11:11:56) : I just plotted the Mauna Loa data over the past 30 years and a linear fit R^2=.9941 vs. a 2nd order polynomial fit R^2=.9983 so the exponential component is very small. What is the source of your cumulative emissions data and what is the uncertainty in that data?

  194. Hockey Schtick (11:47:36) :

    I just plotted the Mauna Loa data over the past 30 years and a linear fit R^2=.9941 vs. a 2nd order polynomial fit R^2=.9983 so the exponential component is very small. What is the source of your cumulative emissions data and what is the uncertainty in that data?

    The difference increases over longer periods: for the full period (1959-2009) of Mauna Loa data the linear fit R^2=.9876 while the quadratic fit R^2=.9992.

    The emissions data comes from IEA/DOE:

    http://www.eia.doe.gov/iea/carbon.html

    the Excel file (1750-2006) can be downloaded from:

    http://www.eia.doe.gov/pub/international/iealf/tableh1co2.xls

    One need to recalculate CO2 to carbon (12/44), Mt to Gt and Gt to ppmv (1 ppmv = 2.1 GtC).

    But there are several others on line.
    Here the one of CDIAC:

    http://cdiac.ornl.gov/ftp/ndp030/global.1751_2006.ems

    They all slightly differ, depending what they include besides fossil fuel use: cement manufacturing, gas flaring, gas losses,… and larger differences are found if one includes land use changes.

    Emissions are based on fossil fuel sales inventories from individual countries by the statistics departments, which are often part of the ministeries of economics. Accuracy somewhere -10/+20% real emissions over the inventories, as sales are probably more underestimated than overestimated. And for some countries (China…) the figures may be largely underestimated…
    I have not included land use changes, as these estimates are quite uncertain, but may add substantially to the emissions.

  195. I voted for “no difference” but would have voted for “Mother Earth is angry, due to its’ life-giving C02 being disparaged and demonized, and it will be necessary to toss 5 of Gore’s Inconvenient Dupes into the volcano in order to assuage her,” had it been available.

  196. George E. Smith:

    Ron House: When diagramming a molecule, one shows how many bonds, not the 3D appearance of the bonds when looking from a particular angle. “””

    Ron, of course I am; and always have been; well at least as far back as about 1950, aware that CO2 contains two double bonds and is a linear molecule, and that it was coventionally represented by O=C=O just as Steve has ita t the top of this thread;

    Sorry I put that badly. I was just making sure less scientifically literate people understood what was going on. That was a very interesting site you referenced, and the 90deg planes of the two double bonds would seem to modify their diagram for the bending oscillation, I would have thought.

  197. You win on this one Steven. I concede that a value in the region of 150,000 tonnes per day is at present the best guess. However, in arriving at your figure of 6 million tonnes over 30 days I believe you make an unwarranted assumption. Please have a look at

    http://news.bbc.co.uk/1/hi/sci/tech/8631396.stm .

    As you can see Mike Burton gives an estimate of the order of 200,000 tonnes per day in very good agreement with your original posting – but for a period lasting “less than a week”. He goes on to say that the volcano was subsequently “much quieter. SO, can we get a better estimate of the period during which it was emitting at 200,000 – 250,000 tn/day?According to the University of Iceland (See http://www2.norvol.hi.is/page/ies_EYJO_compiled) , by 21st April the activity of the volcano had declined by an order of magnitude compared with the “initial 72 hours” indicating that 72 hours or 3 days should be a first guess at the period of maximum emission. Using Burton’s model that CO2 flux varies in proportion to the level of overall activity– which appears to be similar to MacPherson’s model reported on the Breitbart blog – we could be looking at more like 20,000 tonnes per day by April 21st.

    So the total CO2 emission over the 30 days since the eruption began would be a number somewhere between 3 x 200,000 and, 30 x 250,000, in other words 600,000 – 7.5 million tonnes. In choosing a value towards of 6 million in your original posting I do still feel you are cherry-picking. You may feel in return that I’m nit picking, but my concern is that a blog as influential as WUWT should maintain a high level of “data quality”. In particular the urban myths circulating in the past few years about the level of CO2 emitted by volcanoes have been no help at all in bringing about a resolution to the climate change debate.

  198. stevengoddard (19:08:06):

    Steven,
    In my comment sent a couple of minutes ago I neglected to include the comment of yours to which it refers: it is “stevengoddard (19:08:06)”.

    My apologies

  199. JER0ME (07:30:10) :

    I had an article of Moonbat’s sneak up on me while reading the Sydney Morning Herald today. I shall read that journal no more, just in case it happens again.

    He is telling us that the current level of aviation traffic is ‘unsustainable’. Tell Al Baby, and see if he’ll stop…..
    ________________________________________________________________________________

    Sounds like the new variation of the USSR regional passport system. Only those with state permission are allowed to travel.

  200. Ferdinand Engelbeen (11:45:25):
    1) CO2 concentrations HAD to be higher in the past, else dinosaurs and, later, mammoths, mastodons, camels and other animals could not have reached their massive sizes, as I have mentioned in earlier posts. Thus, your final paragraph cannot be correct, it is just a matter of when DID heating, then CO2 rising, happen. Certainly millions of years ago (dinosaurs), probably many times in the past and as recent as within 100,000 years or so (large mammals and carnivores) when the earth conditions were appropriate for this; as has been shown conclusively, earth heats up, Then CO2 is released to peak hundreds of years later.
    2) The diffusion constant is so slow, that your hundreds or thousands of years is not a long enough time frame to observe such a rapid equilibration.
    3) You may believe that CO2 was low in the past. Other proxies show otherwise. It is not belief, but science that is the final arbiter.

    The physics of diffusion, which, BTW I have published and patented extensively over the last 30 years or so, is a physical law. The fact remains: were it true that CO2, as proxies are showing, was 10 to 30 times higher in the past, then the ice core measuring system currently used to measure it would never be able to accurately show the high concentration. And the higher the initial concentration the farther it will fall, over the tens of thousands of years we are talking about. We must find another proxy(ies) to know the true historic values.

    One suggestion would be to measure isotope ratios of another fellow-traveling gas, deposited at the same time, to calculate the relative diffusion rates based on its mass and diffusion into ice. I don’t know which one to pick – CO2 has the advantage of being high concentration in the atmosphere relative to other trace gases, so maybe this is a moot idea.

    However, the ball does not roll uphill. You are right in some of the bases of your argumentation, but the logic does not follow through the entire thread.

  201. bubbagyro (09:02:32) :

    Ferdinand Engelbeen (11:45:25):
    1) CO2 concentrations HAD to be higher in the past, else dinosaurs and, later, mammoths, mastodons, camels and other animals could not have reached their massive sizes, as I have mentioned in earlier posts….
    _______________________________________________________________________________
    Yes, there is such a thing as “stocking” rates. Here on the southeast coast of the USA with CO2 near 400 ppm, plenty of rain, fertilizer, lime and weed control, the stocking rate is about one acre for every 500lbs of body weight. You head to the southwest you start talking X cows (1000 lbs) per square mile.There is no way a planet with CO2 at 180 to 220 ppm could support huge herds of megafauna and that includes the American bison. We are in a CO2 starved era despite all the propaganda.

    Also higher concentrations of CO2 provides plants with more drought resistance. Given colder is drier this is another big issue when it comes to supporting those huge herds. Right now I am praying for rain so my grass will grow. Despite it being spring I have not seen rain for two weeks

  202. Thanks, Gail and Ferdinand, for continuing the discussions, pro- and con-:

    Further clarification:
    As for diffusion, it is certain that CO2 has increased (lagging temperature increase, of course) in the last 18,000 years, or so, through the Holocene, but beginning at a severe minimum at the end of the Pleistocene that must have threatened all life. At 180 ppm, plant life dies. At 5000 PPM, plants grow at amazing rates. It is incredible that AGW enthusiastic scientists, probably because they need to continue gainful employment, discount CO2 minima as root causes for mass extinctions. Of course other events, like the catastrophic Permian extinction was likely caused (contrary to recent “science” TV programs that blame warming) by cooling brought on by the giant Siberian volcanic fissure magma event, since a continuous eruption for 50 or 200 years would obscure most sunlight and kill most plants, but the plants would rebound with the concomitant higher CO2 produced by successive eruptions.

    During the last glacial, 100,000 to 300,000 years would be more than enough time to deplete all historic high CO2 concentration core ice through diffusion, as I mentioned, if I read the Scripps diffusion result correctly. Afterward, from the Pleistocene through our Holocene, equilibration would be back and forth among very low levels, 200 to 400 PPM, for example, in accordance with what Ferdinand was saying. But once the historic Pleistocene reservoir was lost, and since the levels have been low since then, we could never reconstruct the historic high levels with our GCMS simple methods.

    High plant life always equals high animal species. High CO2 = high flora. Low CO2 = extinction. What is hard to grasp about that?

  203. bubbagyro (09:02:32) :

    1) CO2 concentrations HAD to be higher in the past, else dinosaurs and, later, mammoths, mastodons, camels and other animals could not have reached their massive sizes, as I have mentioned in earlier posts. Thus, your final paragraph cannot be correct, it is just a matter of when DID heating, then CO2 rising, happen.
    CO2 concentrations were 3-6 times higher during the Cretaceous, that is the time of the dinosaurs. They started to decline some 40 millions of years ago to the minimum levels seen in ice cores of the past few millions of years. See:

    http://www.geocraft.com/WVFossils/Carboniferous_climate.html

    That was the reason for the evolution of C4 plants (grasses), which need less CO2 and was the main food for mammoths (living in the steppes of the dry North Sea between England and the rest of Europe). 180 ppmv in the bulk of the atmosphere still gives higher concentrations near ground. And most large herds who are mentioned by you are counted in the Holocene, when temperatures were slightly higher and CO2 already back at 280 ppmv.

    as has been shown conclusively, earth heats up, Then CO2 is released to peak hundreds of years later.

    Yes, and at a fairly constant rate: about 8 ppmv/K. Thus an increase of 10 K between a glacial and an interglacial gives a peak of about 80 ppmv (from about 180 ppmv to 260 ppmv). The same ratio is found for the MWP-LIA drop of about 6 ppmv for 0.8 K drop in temperature and the current variability of temperature causes a variability in sink capacity of nature of about 4 ppmv/K on short term (a few years) around the trend.

    2) The diffusion constant is so slow, that your hundreds or thousands of years is not a long enough time frame to observe such a rapid equilibration.

    Wait a minute: the diffusion constant is fast enough to reduce the levels found in the ice cores, but not fast enough to give a flattening of the peak and low levels? Ice cores incluse CO2 in air bubbles at closing time. That may differ somewhat with the atmospheric levels (if there were fast changes in atmospheric composition), but the latest ice at a peak moment will include (near) the peak value. If there was substantial migration afterwards, the levels would go down if the ambient was lower in CO2 than the ice core, or go up if the outside world was higher in CO2. That is basic physics of diffusion. Thus either there was substantial diffusion and peaks found in the ice were much higher in reality and lows in the ice core were much lower in reality. Or there was little diffusion and the ice core record shows the real (but smoothed) CO2 levels of these periods.

    3) You may believe that CO2 was low in the past. Other proxies show otherwise. It is not belief, but science that is the final arbiter.

    As far as I can see, the science shows that ice cores are quite good remains of ancient air, while other proxies are… proxies. But even then, the proxies show similar levels (but with more caveats).

    The fact remains: were it true that CO2, as proxies are showing, was 10 to 30 times higher in the past, then the ice core measuring system currently used to measure it would never be able to accurately show the high concentration.

    The 10 to 30 times was billions of years ago, before even plants existed and before the huge calcite deposits from coccoliths. For the last 40 million of years, levels decreased below 1,000 ppmv (3 times current) and in the last 1-2 million years the levels were below 400 ppmv. The longest ice core represents 800,000 years and shows values between 180 and 300 ppmv. As the levels both go up and down in near exact ratio with temperature (proxies), without smoothing over time, that shows that there was no substantial diffusion through the ice.

  204. Ferdinand Engelbeen (13:28:45) :

    Nice try, but you are caught in a tautology:

    There is no ice core for 40 million years ago, so now you use a proxy? The levels for a couple of million years ago, you use the same ice core we are debating whether accurate or not?

    AND CO2 levels were 3-30 times higher, depending on the “expert” and proxy, not 3-6. The high CO2 levels were not due to the gradual rate you show, and not that high due solely to heating of the oceans, but very high due to vulcanism.

    AND your last paragraph does not hold. Scripps showed that there IS diffusion in solid ice at various temperatures, so saying that there is no diffusion flies in the face of experimentation; but if models are more important to you than observation, then we have little to discuss. We can do proxy battles all day long.

    The rate of trapping of the bubbles is instantaneous, and the rate of diffusion has been demonstrated to be at an appropriate rate to lose high concentrations over millennia. If you will listen to me carefully, the rate will be fast when initial concentration is high, but very slow where there is a low ∂C, such as recently. That answers your quandary how it can be at different rates – it is governed by Fick’s laws. proportional as ∂C/∂T.

  205. Ferdinand Engelbeen (13:28:45) :

    There is no ice core for 40 million years ago, so now you use a proxy?

    For anything older than 800,000 years, we have only proxies. These may be as good or bad as their calibration and the models involved. But that is not the current discussion, the current discussion is if Antarctic ice cores represent the historic CO2 levels accurately, from a few decades ago to 800,000 years ago. Smoothed by gas diffusion rates in firn, but in how far the data are also smoothed (and lowered) by gas diffusion in ice.

    I finally found the full article from Scripps at:

    http://www.igsoc.org/journal/54/187/j07j102.pdf

    Quite interesting, but… also with a lot of assumptions and modelling in it to get to the the theoretical solubility/diffusion parameters of CO2 in ice.

    Some are noteworthy: the theoretical model is based on remelted layers of snow/ice, where much higher levels of CO2 are found (which is normal), but the higher levels are smoothed out over adjacent air in ice layers.

    The chapter near the end is important:
    “Smoothing of the CO2 record in polar ice” shows that temperature is important, where clathrate formation in the deep cores decreases the solubility/diffusion with orders of magnitude:
    Ice cores from colder sites than Siple Dome would experience slower CO2 diffusion in deep ice. The formation of clathrate ice (bubble-free ice) at depths from 500 to 1200m (25–65 kyr) at other Antarctic cold-drilling sites (Vostok, Dome Fuji and EPICA Dome C) is expected to result in highly reduced gas diffusion (Salamatin and others, 1998).

    Vostok at -40 C goes back some 420,000 years (and they stopped drilling far above the higher temperature zone) and Dome C goes back some 800,000 years.

    Thus if there was diffusion, it was much lower in the colder ice cores and far lower back in time beyond 25-65 kyr in these cores.

    More important: in the time frame of 800,000 years, there are different ice cores at different temperatures and accumulation rates, which show similar CO2 levels (less than 5 ppmv difference) for overlapping gas ages.
    See: http://www.ferdinand-engelbeen.be/klimaat/klim_img/antarctic_cores_150kyr.jpg

    According to the theoretical diffusion constants of Scripps, the lower temperature ice cores should show more smoothing for glacial vs. interglacials than the colder ones. But that doesn’t happen. And as said before: layers with lower CO2 (glacials) and higher CO2 (interglacials) should show less difference (for the same temperature -proxy- difference) each 110,000 years further back in time. But that is not observed.

    You see, the real world observations don’t fit the modelled diffusion rates…

    Further, I fully agree with Fick’s laws, based on ∂C. But we differ in opinion about the ∂: you assumed (in the previous messages) that the original CO2 concentration in ice was much higher, but that most of it diffused out of the ice over time. That is only possible with relative high diffusion rates AND if the outside air had (much) lower CO2 concentrations. This even lower than the 180 ppmv observed over very long periods (90% of the time over the past 800,000 years). Again, this is near impossible, as there are also periods where 280 ppmv is measured, at regular intervals.

    Either we have had atmospheric CO2 levels varying between high levels (higher than 280 ppmv) during 10,000 years and low levels (lower than 180 ppmv) during 100,000 years, or there was very little migration. I suppose that it is the latter, as the ratio between CO2 levels and temperature proxy is quite constant over 800,000 years.

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