Little Bubbles part 2 – Firn; The Great Equalizer

Continued from part 1…

Guest Post by Caleb Shaw

Snowflake. Small microscope kept outdoors. Sna...

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I will now tell you what I’ve learned, so you can subject it to your kindly WUWT peer- review. I’m fairly certain I’ve gotten some of it wrong, because it doesn’t entirely make sense.

For the purposes of this paper we will imagine a place where snow falls at a great rate, builds up and compacts swiftly, and turns to ice with little bubbles, in only sixty years.  We will begin sixty years ago, in the year 1951, on an icecap where the temperatures are always below freezing.

When snow first falls it is called, “Snow.”  I find this very relieving, because Climate Scientists have more words for snow than an Inuit.  Their official reason for this is to respect other culture’s words for “snow,” and to demonstrate political correctness, as in Climate Science that correctness is more important than the mathematical sort, and they are exceedingly respectful towards all cultures, except Yankees. (In fact I imagine their secret reason for creating the snow-jargon is to keep Yankee laymen like myself confused, hoping the confusion will keep us from butting in where we are not wanted.  It is almost as if they are saying, “Yankee go home,”  but two can play that game.  With the exception of the single word “firn,” I will only use Yankee lingo.)

The snow that fell in 1951 was dry, and around 95% air,  but wind whipped it around and it became the sort of packed powder that is around 90% air.  At this point the snow is 1951 snow, and the air is 1951 air.

As seasons pass this snow gets buried deeper and deeper by successive snowfalls, as temperatures never allow thawing.  As 1951 turns to 1961, and 1961 turns to 1971, the sheer weight of the snow overhead causes changes in the packed powder.  Despite the fact temperatures never rise above twenty below, the snow behaves as if it had thawed, and becomes “firn,”  which involves the snowflakes becoming crystals of ice too large to be called flakes.

As decades continue to pass and pressures build the firn becomes what Yankee call “gritty snow,” (like granulated sugar,) and then becomes “corn snow,” and finally becomes “candle ice.” Then, in the year 2011, with over 400 feet of snow overhead, we arrive at a momentous occasion, wherein the air in the ice, which once was able to move with some degree of freedom through the firn, is locked into little bubbles. Firn is firn no longer, and has stepped over the frontier and become ice.

I’m sure Climate Scientists have a word for this frontier, but I can only research so long before my computer freezes up, and therefore I’ll make up my own Yankee jargon,  and call the boundary between firn and ice, “The Firnopause.”

It is at the Firnopause that the formerly free air suffers the indignity of an icy chastity belt clamping about its freedom, forcing it to become what Climate Scientists call, “pristine.”  And pristine it must remain, eon after eon, until at long last a gallant Climate Scientist rides up and frees it from its deplorable condition. (Sorry about the purple prose. Unfortunately that is a prerequisite, in Climate Science.)

And that gallant Climate Scientist then discovers a remarkable thing.  As you remember, the snow originally fell in 1951, so the ice around the bubble dates from 1951.  However the air within the bubble dates from 2011. Somehow the air from 2011 has made its way down through over 400 feet of tightly packed snow, and all the air from 1951 has been booted out.

Accepting authority, I try to get my mind around this amazing natural phenomenon, and to think of what natural factors could have caused it to occur.

It can’t be the kinetic movement of air, for that higgiltypiggilty movement would not cause 1951 air to only move up, even as 2011 air only moves down. Even the most frenetic kinetic motion would create a mix of airs from all the years between 1951 and 2011, with air from 2011 the least likely to be down that deep.

It can’t be due to expansion and contraction of summer and winter air, because, once you move down ten feet  into the firn, temperatures remain constant, and air neither expands nor contracts.

The best solution involves the difference between a huge 950 mb winter storm and a huge 1040 mb winter high pressure area.  Before my computer froze I determined this was a difference between 13.778 psi and 15.084 psi. (I haven’t a clue what this means in terms of volume; the peer-review of WUWT will help me out, I’m sure.)  However, because I prefer math to be simple, I will state there is a ten percent difference in volume between  the same amount of air in a 950mb low and a 1040mb high.

This is a significant difference.  Stand by a cave with a large chamber and a small entrance as barometric pressures falls,  and you will feel a breeze blowing out.

A cave is actually a poor analogy for firn, for firn in effect has a large entrance which funnels down to smaller and smaller cracks and capillaries.  However, just to shut me up, assume that, as a 950mb low gives way to a 1040 mb high overhead, air actually can be inhaled 10% of the way down into the firn.

Big deal. That is only 40 feet, and leaves you with 360 feet to go, for 2011 air to be at the Firnopause in time to be clamped into little bubbles. Furthermore, as soon as the 1040 mb high starts to move off and pressures fall, the 2011 air gets exhaled out.

Obviously we need to discover a way to inhale the 2011 air down, and exhale all the pre-2011 gas out.  Fortunately Climate Science is much like undone homework; if you have no excuse you can always make one up.

Therefore, to be helpful, I have invented the concept of “grabacules.”  Grabacules are yet-to-be-discovered, gravity-activated, kinetic bonds on the sides of fresh air,  but worn off the sides of stale air.  Because they are gravity-activated, 2011 air slides freely downwards through the firn, but grabs onto the ice when any power tries to move it back up.  In essence 2011 air stands aside for pre-2011 air, (which lacks grabacules,) to pass, and then moves downwards again the next time downward forces come into play.  The 2011 air moves like an inchworm, moving foreword, grabbing, and moving foreword again.

Pretty cool theory, aye?  Isn’t Climate Science wonderful!?  (And if you think  that idea is good, you should have heard my excuses for undone homework. A breathless hush would fall in the classroom, as I arose to speak…)

The problem with my admittedly brilliant idea is that the inch-worm gets shorter and shorter.  Moving 10% of the way to your goal can never get you to your goal.  Up at the surface of the firn, a huge change in atmospheric pressure may shove the 2011 air 40 feet downwards,  but 100 feet from the firnopause the same change only moves the 2011 air 10 feet towards the goal, and 10 inches from the goal it only moves an inch towards its goal.

According to my layman’s calculations that is as far as the 2011 air gets, for by then it is 2012, the 2012 Air starts downwards, and the 2011 air, its grabacules all shot to heck, has to U-turn and start back upwards to make room for the 2012 air.

This leaves a space of nine inches the 2011 air never gets to.  This is a very important space, for it is this air which is actually is incorporated into the little bubbles.  If this air isn’t 2011 air,  what is it?

First we must have a name for this nine inches, just above the Firnopause, and I suggest it be called the Yankeeopause, (named after me, of course.)

It is in this nine inches which a factor so tiny it is unseen, up at the surface,  becomes glaringly apparent.  It is a factor I call “Spongeosis.”

We all know that, when you squeeze a sponge, water comes out.  The exact same thing happens when you squeeze snow, which is 95% air, and wind up with the Firnopause ice, which is at best 10 % air.  The difference is that with a sponge you squeeze out water, but when you squeeze snow you squeeze out air.  Where is that air to go?  Nowhere but up.

This very weak, nearly imperceptible flow is unseen at the surface, where changes in barometric pressure have veritable tides of air inhaling and exhaling through the firn,  but down in the quiet and still depths of the Yankeeopause, this flow is all there is.  Like the bow-wave of a boat, it moves just ahead of the freeze-up at the Firnopause, and consists of the very last bit of air squeezed from the snow.  It never holds air from above, and rather consists of a great many years worth of air all slowly pushed ahead like snow before a plow.  Some of the air may be centuries old,  and when a part of the Yankeeopause’s blended air gets left behind as a bubble in ice at the Firnopause,  the CO2 level in that bubble will not represent any particular year,  but rather an average.  All peaks and valleys in the CO2 record will be smoothed out.  The firn, in the end, has been a great equalizer.

And that is the end of my story, which I have told for your entertainment.  It flies in the face of the desire of Climate Science, which is to move 2011 air down to inclusion in tiny bubbles at the Firnopause.  However it’s my story, and I’m sticking to it.

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161 thoughts on “Little Bubbles part 2 – Firn; The Great Equalizer

  1. It’s a nice story, but it appears to contradict something that I believe is true of snow being compacted to ice. The process does a respectable job of preserving surface temperature history at the site, which would be difficult to do with the uppermost 400 feet breathing in and out and mixing air with ice and snow. At least glacier accumulation does a far better job of recording temperature history than does thermal conduction into soil or rock.

  2. That is a very good story with an interesting ending. I enjoy the naming of the Firnopause. Apt and accurate.. No grants for your esteemed research and transcription though . . . I imagine. Big Boots you tread well in !!

  3. If that is your story and you are sticking to it then maybe there is hope. The hope is that some “climate scientist” will explain why Yankeeism and spongy-ism are not part of ice core lore. I suspect there is a YAD06 buried in some little bubble waiting to show its effervesce. Maybe we need some professor from Penn State to explain it all.

  4. I believe you have captured the essence of what happens. From you description the top 40 feet breaths in and out as low and high pressure systems pass over. The bottom layer of this top 40 feet ends up with “present day” air. However the lower 360 feet moves up and down by ever decreasing amounts and gets slight mixing through the years, resulting in the trapped air being a mixture of potentially several hundred years of air.

  5. Well I for one am disappointed.

    Here I was, settling in for a great read about chemistry, physics, and how they relate to raising daughters.

    Seriously, a great read. Is the raising daughters part done or will it be continued in Part 3? Inquiring fathers want to know…

  6. Take a look at Antarctic Ice Cores: The Sample Rate Problem (Middleton) WUWT Jan 1, 2011.

    Any my thoughts at 1/2 11:12 pm.

    The de-flating of the air column during compation is similar to the dewatering of shales during lithofication. Looking at the physical processes, the blending would seem to be total. That make all the more astounding that you see varying concentrations of CO2 in different layers of ice, and apparently with some regional and world wide correlation.

  7. I like the mechanisms you firnished. I think glacial gas dating is now well and truly firnished as a respectable field. Kudos!

  8. Although there might be some bulk flows associated with outflows from compaction and changes of barometric pressure, the exchanges of gases above the “firnopause” should be dominated by diffusion processes. For example, for CO2 in air at the freezing point of water, the diffusion coefficient is about 0.14 cm^2/s. In sixty years, CO2 molecules could move diffusively about 400 meters, which is about three times the depth to your firnopause. The conclusion should be that the air trapped at the firnopause would have properties intermediate between those of air at the time the snow fell and those at the surface above the firnopause.

  9. “It would appear that Climate Science is easy to do.”

    Indeed. Plug it into a model, and it becomes as rigid a fact as science can ever create.

  10. Off-topic but appropriate comment from the past. Will Rogers: “It’s all right to fix the world, but you better get your own smokehouse full of meat first.”

  11. It would seem that as the air is deflated from the compacting firn, it would be thoroughly mixed — IF it rose vertically in a 1 D model.

    Let’s take a couple of facts and an analogy with shale dewatering.
    Fact 1: the snow is in layers, at least as frequently as annually, and perhaps as frequently as each storm. The water content of the snow is not constant within a storm, much less year long.
    Therefore the snow column is not uniform.

    Fact 2: as the snow compacts, these non-uniform layers will have slightly different compaction rates and therefore, different permiabilities to air flow.

    Analog: When shales compact and dewater in the lithification process, the water is believed to migrate horizontally toward the more permiable sands, which are in communication with faults or other points of dewatering leakage.

    So as the firn compresses, air that is mostly the same age is squeezed out and diffuses from locally high pressure impermiable layers into permiable layers laterally to a vent.

    I think this is a way to maintain a difference in air chemistry in a relatively short vertical distance.

    This mechanism does not address concerns about molecular sieve and the potential for CO2 solubilty at the surface of ice crystals or adhesion to dust in the ice.

  12. I spend a lot of time in snow, and can tell you that the barometric lungs are alive and well.

    I ski a mountain known as Mt Bachelor in Oregon. It looks like a mountain, but actually. it is just a really big pile of volcanic cinders, poorly held together by some lava flows. Every winter it gets covered by about 20 feet of snow.

    When air pressure rises, air moves into the gravel pile, where it is warmed to the average annual temperature, which I will make up on the spot,(like 97.36 % of all statistics cited) —-44 degrees

    When air pressure drops, the warm air flows out, melting the snow. It frequently follows a particularly permeable route, and gushes to the surface, melting out a vertical cavern in the snow. Skiers fall into these pipe shaped hazards.

    I don’t know the depth of mixing, but if you throw in some osmosis, maybe some convection, a few more scientific terms, it could be said that a lot of mixing goes on.

  13. But if tiny bubbles are discredited then we would have to rely on plant stoma records and Becks empirical measurements. The problem with Becks historical chemical CO2 measurements is that they are ground level measurements that were recorded by hand using lest precise methods than available today, much of the data is too noisy to show a trend and many of the measurements may have been corrupted by proximity to built up areas and industry……oh wait, climate science should be ok with that. We’ll just apply the BEST methodology. What could possibly go wrong?

    sarc/

  14. So – in 50-60 years, the snow/ice becomes compacted enough to wall off bubbles and prevent diffusion, which as bones noted is fast enough to exchange with the surface of the snow quite well. So the bubbles in the ice have about a 60-year average level of CO2, oxygen isotopes, etc.

    Well, that’s about what the ice guys have always said – 60 years for places with lots of snow, longer for those with less (like the ‘desert’ regions of Antarctica).

    Two posts, lots of “oh shucks” prose – but missing the diffusion rate. Not a big story, C. Shaw.

  15. You might be leaving out a few other processes which are known or suspected to be occurring once the air bubble is trapped.

    The first of these is diffusion of the gases out of the bubble through the spaces between the molecules in the crystal structure, which while it happens very slowly, does occur. It also occurs at different rates for different constituent gases within the bubble and for different isotopes within those gases.

    In addition to diffusion through the crystal itself, there is transport of gases (and liquid too) between ice crystals along the boundaries between the crystals. We know this must occur because at depth within the ice are bodies of liquid water.

    Another thing that occurs when ice cores are brought up to the surface – Microfractures. These are a product of decompression when deeply buried ice is brought up to atmospheric pressure. Seems those trapped gases are under pressure when buried deeply within the ice sheet and the ice is not strong enough to fully contain them during decompression.

    Finally, and this one kind of shocked me when I learned of it, the drill bits for ice rigs are lubricated with diesel fuel. I wonder what this does to gases now connected to the ice core surface via microfractures.

    Add up all the possible issues and what do you get? I’m pretty sure the answer is NOT a pristine sample of the atmosphere from some time in the past.

  16. Very nicely done. A fine model and not an untestable prediction or conclusion in the lot. Way to much physics and chemistry for the climate guys to even begin to understand, however.

  17. From Convective mixing of air in firn at four polar sites, 2006.

    The top 1–20 m from the surface may be the convective zone in which convective mixing overwhelms molecular diffusion and prevents isotopic fractionation.

    The second zone is the diffusive zone, the largest part (40–100 m) of the firn, in which molecular diffusion dominates the gas movement and thus gravitational and thermal fractionation occur.

    The third zone occurs in the bottom 2–12 m and is the lock-in zone

    The paper describes how the firn air was sampled and describes the results. This paper addresses most of the speculation above.

  18. It has always been clear, at least to engineers who spend their every waking moment teasing signals from noise, that the gas trapped in the ice bubbles must be an amalgum of the years before (gasses drifting up) and the years after (gasses drifting down) the “age” of the ice at the target layer. You can envision a probability density function in Y, probably unusually shaped, centered on the target ice layer (historical age) in question where the amplitudes of the density function above and below the target layer represent the contribution of gasses to the target layer from the adjacent layers. The spread of that function, similar to line spreading in lasers, determines the minimum temporal distance between layers that can be used as markers to ensure independence of each data point. The questions I have are 1) what is the shape of that distribution function and 2) how wide is the line spreading? 6 years? 40 years? 200 years? 1000 years?

    The line spreading determines the minimum temporal resolution that can be expected from that sample. That time resolution becomes the minimum viable sample clock in the data and no artifact faster than that clock can be assumed to be valid. Technically, to prevent “aliasing” which is the translation of the amplitudes of frequencies higher than the sample rate into the lower frequency space, the data must be run through a low pass filter having the sample clock frequency as the cut-off frequency. As well, the data must be de-convolved with [Sinc t] to eliminate the end effects of the first and last few data points. The “end effects” are one of the frequent points of discussion on climate sites but I have never seen the [Sinc t] deconvolution requirement mentioned even once on any site. This raises the question of whether it is being done. Is there a reason it should not be done?

    I can only assume that the “ice scientists” have properly worked this problem and have a proper answer. The next step, Caleb Shaw, is to follow that layer of ice from the drill stem to the lab to the computer and finally to the graph to estimate an expected accuracy and resolution of the final plot.

  19. In the comments section of “Little Bubbles part 1″ I was chastised for name calling (although I consider the term I used an endearment for someone who is hopelessly conflicted).

    I deserved the chastisement. I apologize. Thank-you moderator for your efforts in keeping the discussion civil.

    That said, heres my further contribution.

    I say never mind all this talk about clathrates and super-cooled water. What do we know about algae, living just under the surface of a translucent layer of snow – this will be a quite balmy microclimate by Arctic/ Antarctic standards. And these algae will be quietly photosynthesising and drawing down the levels of trapped atmospheric carbon dioxide that is destined to be bubbled once it reaches the Firnopause?

    Have any of the bubble scientists actually checked their ice cores for the microscopic remains of bacteria, yeast and algae that might have lived in the snow? What about sampling for microbial DNA and RNA in the ice layers? If one were to get evidence of organic materials in the bubbles, might this not cast doubt on bubbelisation as a proxy for actual levels of carbon dioxide in the atmosphere? It is logical to assume that photosynthesis and respiration will have an effect on carbon dioxide concentrations under the snow if the microbiota are present, isn’t it? Trouble is that no one seems to look for it.

  20. Your explanation makes as much sense and is more entertaining.

    However you missed the problem that the snow when compressed not only forms ice but also water that can absorb the CO2. CO2 measured in the melt water at the firn can be as high as 12,000ppm (Stauffer et al 1985)

    Also after 1985 only the CO2 in the bubbles is reported while the data before 1985 (Higher results) also looked at the CO2 in the ICE SURROUNDING the BUBBLE.

    http://www.co2web.info/stoten92.pdf (Jaworowski & Segalstad)

  21. Snow is curiously porous. I’ve been inside a snow cave with the entrance blocked off with snow. I could still feel the wind blowing through.

    So. A few issues. I don’t find any references to a pore closure depth (a.k.a. firnopause) of 400 feet (120 metres). The usual closure depth I find is more like half of that, 170 to 200 feet (50-60 metres).

    As to the age of the air mixture, a combination of diffusion, changing barometric pressure, changing temperature, and wind pressure will make the final air some weighted mixture of all the air from the time the snow fell until the pore finally closed. My guess as to that weight is that the ongoing interchange will weight the age to something nearer to the time of pore closure than the time the snow fell.

    One final point. Regardless of the weighting of the ages of the different air in the bubble, we are sure that the air will not be composed of air from the years around when the snow fell. Almost all of that air will be gone, mixed out in the decade after the snow fell. This means:

    • The ice age (age of the ice surrounding a bubble) will always be older than the air age (weighted average age of the ice in the bubble).

    How much older? The mixing seems to go on until close to the pore closure time, which in turn depends on how fast the snow falls. Scientists do think about this stuff …

    w.

  22. Firnologists are airheads. Bubbles in the brain cause strokes. Strokes cause mental and physical disabilities and blindness. Hence, …

  23. I like the ‘grabacules’ theory … a possible explanation for why the bottom sheet on my bed rides inexorably up towards the pillow end most nights. [Important legal note: No daughters are involved in this process.]

    But yes. And once all the little bubbles have sealed off with their ???-year old air mixture, presumably all chemical and physical interaction with the surrounding ice must stop, or those future noble climate scientists would only end up measuring a long-term average of an approximate equilibrium condition. Then they’d have to conclude that historical levels of, say, CO2 were very stable and (with all that pressure involved) probably relatively low.

    Errr … remind me, someone. What are they actually saying?

  24. Snow falls as 95% air but the time it is ice it’s < 5% air. So below the breathing zone air is being squeezed up past newer snow as it compresses. So the air in the trapped bubble is *older* than the ice around it.

  25. Climate science begins as Bogus Suppositions (referred to hereafter as BS); as seasons pass, this BS collects and gets deeper and deeper. As First Assessment Report turns to Second Assessment Report, and Second Assessment Report turns to Third Assessment Report, etc, the sheer weight of the BS overhead causes changes in the impacted science.

    Despite the fact the data do not reflect the posited suppositions, the BS behaves as if it had been validated, and becomes “consensus”.

    Then, in the Fifth Assessment Report, with over 4000 feet of BS and lots of flakes overhead, we arrive at a momentous occasion, wherein the money in the economy, which once was able to move with some degree of freedom, is locked into huge grants, science is science no longer, and has stepped over the frontier and becomes “settled”.

    I’m sure Climate “Scientists” have a word for this frontier, but I can only research so long before my brain freezes up, and therefore I’ll make up my own jargon, and call the boundary “The MANNopause”.

  26. Their official reason for this is to respect other culture’s words for “snow,” and to demonstrate political correctness, as in Climate Science that correctness is more important than the mathematical sort, and they are exceedingly respectful towards all cultures, except Yankees.

    Now, that was uncalled for, that scientists use their lingo to be “politically” correct. You could have come up with all kinds of reasons, but this is bullshit. Their behaviour has nothing to do with PC and it just shows bias. You don’t accept other things as fact, you need to question your aversion to PC (or question your concept of PC, to be more precise).

    And by the way, what the heck is wrong with being respectful towards other cultures? Especially when you are from the White/Christian/European culture and the other culture has been the target of subjugation and/or extinction in the name of your culture?

  27. And all this “I’m just a naive boy from Texas asking simple questions” just reminds me too much of “A Modest Proposal”. Only, you seem like the target of the satire, not the author.

    Stick to (climate) science, and by all means write funny about it. It is really good to read critical/sceptical positions, that you don’t take something for granted (“Everybody knows CO2 will kill us all!”). Don’t bring positions into it you haven’t critically/sceptically questioned and researched yourself (“Everybody knows that PC is bullshit!”).

  28. Konrad

    Caleb explains the firn scenario in a much more amusing manner than I did in my article;

    http://noconsensus.wordpress.com/2010/03/06/historic-variations-in-co2-measurements/

    However it is not correct to say that the methods of measurements of Co2 from 1820 (around the date of the first credible readings) up to the 1940s, immediately prior to Keeling, were not scientically determined.

    Some very famous sciemtists took measurements with well tried equipment and were well aware of the dangers of contamination from adjacent co2 emitting sources. The British enacted the first legislation to set co2 limits (in cotton factories) over 120 years ago and such parameters as the gas light burners in a factory had to be accounted for.

    There are too many historic measurements to be dismissed, and an audit of the more robust readings by a suitably independent and qualified authority would settle the matter once and for all.
    tonyb

  29. Sandy says

    “Snow falls as 95% air but the time it is ice it’s < 5% air. So below the breathing zone air is being squeezed up past newer snow as it compresses. So the air in the trapped bubble is *older* than the ice around it."

    Surely the 'old' air would change the composition of the newer air in the layers above it?
    tonyb

  30. bones:

    Thankyou for your clear explanation (at November 1, 2011 at 9:06 pm ) of a point I have made repeatedly in many places (including on WUWT) since the mid-1990s. Indeed, it is the major disagreement on ice core data between Ferdinand Engelbeen and myself.

    To save others needing to find your excellent post, I copy it here; you wrote:

    “Although there might be some bulk flows associated with outflows from compaction and changes of barometric pressure, the exchanges of gases above the “firnopause” should be dominated by diffusion processes. For example, for CO2 in air at the freezing point of water, the diffusion coefficient is about 0.14 cm^2/s. In sixty years, CO2 molecules could move diffusively about 400 meters, which is about three times the depth to your firnopause. The conclusion should be that the air trapped at the firnopause would have properties intermediate between those of air at the time the snow fell and those at the surface above the firnopause.”

    Yes!
    And the IPCC says the firn takes 83 years to seal. Assuming this 83-year figure is correct, then the effect of diffusion in the firn is similar to the effect of a 83-year running mean conducted on data from ice that sealed in each single year.

    It is not possible to conduct an 83-year running mean on the Mauna Loa data for atmospheric CO2 concentration because that data only started to be obtained in 1958 (i.e. about half the time ago of 83 years).

    And the ice core data is consistent with the fluctuations in atmospheric CO2 concentration assembled by Beck if an 83-year running mean is applied to Beck’s data.

    Simply, if the IPCC is right that the ice takes 83 years to seal then the ice core data cannot indicate significant fluctuations in atmospheric CO2 concentration of less than ~160 years duration.

    Richard

  31. It certainly is a very interesting thing you talk about there, how air is trapped in ice and what air is actually trapped.

    If we consider your example that it takes 60 years going from snow to ice the question is, the air between 30-60 meters, does it ever escape out in the atmosphere or is it forever trapped in the ice and blended with the air from the layers above?
    In that case the air that gets trapped could actually be a mix of hundredes, instead of a decade or two. In that case CO2 swings that last for 100 years could be averaged out in the past and become mostly invisible.

    This must have been calculated and done som research of allready how much air that is trapped and blended with comming years.

    At what depth is air permantently trapped in the snow, not ice, and do not escape into atmosphere anymore but can stll blend around in the compressed snow?

    How many % air does the ice samples contain? By looking on some pictures it looks like there are just a few percent air in the ice.

    Lets make a thought experiment with guesstimated values.
    If the ice contains 4% air bubbles per ice volume, and new snow contains 95% air it means that about 96% of the air for any given year gets blowed out inte atmosphere by the previous 60 years of remaining air.

    So for any given year of air in the ice it must consist of 96% old air and 4 % of that specific years air. This value is proboably much smaller since the air gets blended with the previous and comming decades. It may never exeec 1% for any given year. This could probably be calculated by someone how knows how to do it.
    Since the air blended and gets pushed upward it doesn’t mean it takes 60 years for the air to get trapped completley as this is probably a logarithmic blending where not all 60 year old air gets trapped but some portion gets blended with above decaeds and can surive beeing trapped for hundreds of year.
    Any given year should have a higher portion of air blended in from the closest decades than air from 50-60 year old snow. Even air from comming decades will blend into the past as the blowing outward is very slow and air can mix rather fast if it can move in any way.
    I can’t make any conclusions from my own thought experiment but it certainly convinces me that this is someting I am interested to read more about.

    Am i completley off in this subject? Does anyone know of any research that is available and readable for a layman like me?

  32. When a temperature profile is taken through a glacier the temperature gradually increases towards the base to 0C or just above due to geothermal heat. The same will happen through an ice sheet. Perhaps this gradual warming helps change the air.

  33. Caleb,

    Great post. I have always wondered how they resolved the gas diffusion/resolution issues in ice cores but have never looked into it.

    I think what you are looking for, though, is brownian motion and fractional vapor pressure as the mechanism for transport. I think calling it ‘2011 air’ vs. ‘1951 air’ is a bit of a misnomer. What is looked at is air that has the same chemical composition as the atmosphere had in 2011. While it would be impossible to replace the air, hundreds of feet down into the snow/ice strata, nature will ensure that, over time, the co2/nitrogen/o2, etc become balanced out. It probably becomes less effective at doing so as the snow finally makes the transition to ice, someone with a deeper understanding that I have would have to do a lot of math to be able to define that, but the mechanisms of brownian motion and fractional vapor pressure will ensure that the various gases equalize, over time, even at great depth.

    Sorry if someone already posted this information, but I didn’t have time to read every comment.

    Anyway, it’s still a great post.

    Google dalton’s law, brownian motion, mass diffusion and Einstein’s theory (not relativity).

  34. So diffusion dominates compaction outflow, ok.
    Could the nuclear test of the 60’s be used as a marker to see how wide the diffusion is??

    It seems compaction should be at a certain depth, so double the accumulation rate (say PDO flip) halves the enclosure time??

  35. Concerning Ernst-Georg Beck’s analysis of historical CO2 data:
    I wrote with Beck as co-author a paper on the accurate determination of CO2 background levels. The CO2 versus wind speed method whih gives good results for contemparary measurements was also applied to historical measurements (Liege, Giessen, Vienna) and gave as a conclusion that these calculated backgrounds were clearly higher than those of the IPCC consensus (i.e. derived from ice core bubbles).

  36. I thank commenters for their responses. My intent was to get people to chuckle about things they often take too seriously, but also to think about the mixing that occurs before bubbles form. Most are focused on the possible mixing that occurs after the bubbles are already formed.

    I learn a lot from people. The entire subject of algae and bacteria living in the snow is fascinating, and something I was not considering.

    I likely need to go back to school regarding the subject of diffusion. Perhaps we could persuade a great teacher, (such as Willis,) to lecture laymen like myself on the subject. However, even if 1951 air can move 900 feet in sixty years, it still doesn’t address the issue of it all mysteriously heading up, as 2011 air all mysteriously heads down, which was what I was poking fun at. I remain convinced the air in the bubbles is a blend, right from the start.

    I’ll have more comments, but I need to milk my goats, and do other chores.

  37. Jerker Andersson says:
    November 2, 2011 at 2:53 am

    …I can’t make any conclusions from my own thought experiment but it certainly convinces me that this is something I am interested to read more about.

    Am i completely off in this subject? Does anyone know of any research that is available and readable for a layman like me?
    ___________________________________________
    There is this readable paper: http://www.co2web.info/stoten92.pdf

    You could also read the pdfs on Segalstad’s web site: http://www.co2web.info/

  38. Considering we are talking about CO2 so the 5% air buble contains about 0.03% CO2 and add the impact of the differences in partial pressure of CO2 and other gasses into the equation over the time, the time stamp of the CO2 content in the bubble becomes at best a wild guess.

  39. A simpler explanation for the air-ice age difference is that modern air migrates into microcracks in the ice cores. These cracks result from the expansion of air as the pressure of all that ice above is removed. Two observed facts support this idea. One, the measured air-ice difference increases with depth from about 80 years at the “fern” to over a thousand years at depths. Two, carbon 14 has been detected at depths where it should not be detectable. Click on my name for more details.

  40. Dear Caleb,

    I am a little disappointed. I expected a firm proof that countered the conventional wisdom of why ice core bubbles are not reliable. But all what I see now is that you haven’t read the relevant items in the literature.

    Nobody in the ice core world says that air enclosed at 72 meter depth (that is where the Law Dome ice cores are sealed off from the above layers) has the same composition as in the atmosphere of that moment. That is only the case for the upper 10 meters (at Law Dome, different for different places and circumstances). Below that, there is a “stagnant” layer where only diffusion is at work, diffusion you don’t mention at all? The diffusion speed depends of temperature and pore diameter and of course goes in both directions. That is nicely explained at:

    http://courses.washington.edu/proxies/GHG.pdf

    One can use a diffusion model to calculate the theoretical mixture of gas ages at closing depth, as was done for the Law Dome ice cores, but the model calculation was confirmed by Etheridge e.a., 1996, by measuring CO2 levels in firn at different depths, top-down until closing depth for one of the ice cores:

    The average gas age at closing depth was 7 years older than the air at the surface:

    with a huge, assymetric distribution of gas ages as can be seen in the graph nr. 11 of the first reference.

    The end of the story is that, while there is averaging at work, the averaging is far smaller than the 40 years that the gas exchange is possible (the bulk is at +/- 5 years around the average gas age) and any peak value of more than 20 ppmv during 1 year or 2 ppmv sustained over 20 years would be detected in the Law Dome ice cores. Still, you haven’t shown any proof that the ice core measurements aren’t reliable…

  41. John West says:
    November 1, 2011 at 10:43 pm

    The reference you gave only shows that the resolution of the ice core (the averaging over a period) theoretically broadens from 20 years to 22 years at some depth to 40 years at full depth (at 70 kyr age). That is all. Thus the resolution gets worse with migration, but that doesn’t change the average level over that period. For much colder ice cores like Vostok and Dome C, that is even unlikely, as there is no change in CO2/temperature ratio over each glacial/interglacial period 8 times 100 kyr back in time. If there was the slightest migration, the ratio would fade over time, as 90% of the time the temperature/CO2 levels are low and only 10% of the time they are high.

  42. Richard S Courtney says:
    November 2, 2011 at 2:04 am

    And the IPCC says the firn takes 83 years to seal. Assuming this 83-year figure is correct, then the effect of diffusion in the firn is similar to the effect of a 83-year running mean conducted on data from ice that sealed in each single year.

    Dear Richard,

    The age distribution of the air at start closing depth is not a running average of the years to date, as the average gas age is much younger than the average of years to sealing. For the 40 years to sealing in the high accumulation Law Dome cores, the average age is 7 years, not 20. For the 600 years to sealing of Vostok, the average age of the gas at sealing depth is about 60 years, not 300. Thus the age distribution is quite assymetric, with relative much young air and a long but small tail of old air.
    See the age distribution map for the Law Dome ice core of Fig. 11 at:

    http://courses.washington.edu/proxies/GHG.pdf

    That graph shows that a 80 ppmv peak around 1942 as the late Beck’s data shows, would be detected in the high resolution Law Dome ice cores as an 8 ppmv peak value for the gas age of that period. And detectable over a period of more than 20 years.

    Further, there is an overlap of about 20 years between the Law Dome ice cores and direct measurements at the South Pole, within the accuracy of the ice cores…

  43. Richard S Courtney says:
    November 2, 2011 at 2:04 am

    And the IPCC says the firn takes 83 years to seal.

    At Vostok, the air is 1,000 years to 5,000 years older than the ice. (It varies depending on how much snow falls per year.) Now that’s a smoothing filter!

    On top of that, CO2 is sampled by crushing 40 grams of ice and measuring the released gas. The references don’t say how many years that represents. But it is clear that no one is sampling the air in a single bubble.

  44. I have wondered about this in another way. If CO2 can diffuse from the air bubble into surrounding ice, how much negative bias (CO2 concentration may be much lower than measured) is inherent in the process. I am confident that there have been some studies that consider this and offer corrections…can anyone give me a cite?

  45. OK, now for some fun.

    I have made it clear elsewhere that I’m not a scientist. I lacked the discipline necessary for science, and have an unruly imagination. I chose “The Arts,” and not “The Sciences.”

    I have great respect for true scientists, and would never be so rude as to tresspass on their territory, but they started it. By that I mean Climate Scientists left the strict confines of science, and tresspassed on my turf, which is the land of fiction, as opposed to fact. If they are going to so rude as to come horning into my landscape, well, I am going to defend my space.

    I was talking with my eldest daughter this morning about all the reponses I got, when I brought up daughters in part 1. There is even some disappointment I didn’t bring daughters into part 2. She got quite a chuckle that I got 40 responses about daughters in a thread about icecores.

    However I believe this demonstrates something. I believe it shows Climate Science (like Sociology and Psychiatry,) have wandered outside the strict confines of science, and have abandoned the strict discipline, and have entered the land of romantic mush. Sorry, fellows, but that is my turf. Don’t go there, unless you want to leave yourself wide open for some serious tweaking. If you don’t have a sense of humor, and can’t take a joke, go home.

    Either that, or just be honest, and renounce science. Announce you have decided to be a “Social Reformer,” and we can duke it out as equals. This business of hiding behind the father’s leg of Science while picking a fight is not very grown up.

    (The post “Thank You, Matt Ridley” is great. It describes psuedoscience and confirmation bias supurbly. Study it, and weep, (or preferably laugh.))

    I know a lot about childish behavior, because we run a child care at our farm, teaching children the grim truth: Eggs don’t come from supermarkets; they come from the butt of a chicken. Carrots don’t grow in plastic bags; they grow in dirty dirt. It amazes me how many don’t even understand this simple science, these days.

    Instead we have people who walk around thinking they are scientific, with their head in the clouds. They need to be tweaked. There needs to be a clear distinction between Science and “the Arts.”

    I have more to say about tweaking, but have to run children to the local kindigarden.

  46. Francis Massen says:
    November 2, 2011 at 5:22 am

    Dear Francis,

    Some time ago we had some discussion about this point… I fear that the Giessen data are not reliable at all (method, apparatus, sampling?), but besides that, there are too few data points and with a high spread, at high wind speed only (about 20 datapoints at over 4 m/s wind speed) to make a reliable prediction with your method… The same problem for the Liège data (although these have a smaller band) and the Vienna data still have a huge spread (290-380 ppmv) at over 4 m/s still wide at 10 m/s and beyond.
    Thus I like to see the error band of the prediction for few points and/or huge bandwidth at high wind speed…

  47. We have human artifacts with verifiable provenance in the ice from 40+ years ago. Can’t we just dig one of them up and measure the gas content of the ice right next to it? Hasn’t this been done? There’s also carbon dating to compare to ice gas content. I don’t understand why this is being treated as a purely theoretical issue, when experiment is clearly possible.

  48. Doug in Seattle says:
    November 1, 2011 at 10:21 pm
    [….]
    Finally, and this one kind of shocked me when I learned of it, the drill bits for ice rigs are lubricated with diesel fuel. I wonder what this does to gases now connected to the ice core surface via microfractures.
    [….]

    T.C. says:
    November 1, 2011 at 10:59 pm
    [….]
    I say never mind all this talk about clathrates and super-cooled water. What do we know about algae, living just under the surface of a translucent layer of snow – this will be a quite balmy microclimate by Arctic/ Antarctic standards. And these algae will be quietly photosynthesising and drawing down the levels of trapped atmospheric carbon dioxide that is destined to be bubbled once it reaches the Firnopause?

    Have any of the bubble scientists actually checked their ice cores for the microscopic remains of bacteria, yeast and algae that might have lived in the snow? What about sampling for microbial DNA and RNA in the ice layers? If one were to get evidence of organic materials in the bubbles, might this not cast doubt on bubbelisation as a proxy for actual levels of carbon dioxide in the atmosphere? It is logical to assume that photosynthesis and respiration will have an effect on carbon dioxide concentrations under the snow if the microbiota are present, isn’t it? Trouble is that no one seems to look for it.

    There are a number of research studies which have looked at the question of biological activity and biological contamination of ice core samples. Brent et wanted to study decontaminaton protocols for returned samples of extraterrestrial samples, and discovered the Vostok ice cores were extensively contaminated by reference strains of biological markers, biological contaminants in the diesel fuel used as the driloling fluid, and other biological contaminants. See:

    Brent C. Christner, Jill A. Mikucki, Christine M. Foreman, Jackie Denson, John C. Priscu. Glacial ice cores: A model system for developing extraterrestrial decontamination protocols. Received 15 February 2004; revised 8 September 2004.

  49. Ferdinand Engelbeen says:
    November 2, 2011 at 6:49 am
    [….]Still, you haven’t shown any proof that the ice core measurements aren’t reliable…

    It is unscientific to ask anyone to “prove” a negative proposition. It is up to the climate scientists to demonstrate by a preponderance of the evidence that the air recovered from the bubbles of air in the ice are relatively unchanged in composition before and after sampling in the ice cores. This task they have so far failed to do, because there are far too many unresearched and unscientific assumptions incorporated into their conclusions. They would serve the scientific community better by acknowledging the true extent of what they do not know than asserting without adequate evidence that which they claim to know.

  50. Having conducted some experiments involving gas-solid diffusion, I have an alternate hypothesis for the bubbles in the ice: The bubbles are mostly not from the atmosphere at all. All of the atmospheric gases have either escaped back up into the atmosphere, or are in solution in the ice, where pressure can cause them to accrete in the grain boundaries (ice being a mineral with a crystal structure). So where do most of the bubbles come from? From the underlying rock that the mass of ice is sitting on. The ice is not static, it is constantly moving, and thus it is constantly grinding the surface of the rock. The particles of rock become a very thick slurry with the ice, and the resulting combination leads to the rock giving up some gases, which rise slowly through the ice mass as very small bubbles (gas-solid diffusion). Therefore, the gas bubbles detected have very little to do with the atmosphere, and a lot to do with the underlying rock.
    It is just like that with teenagers: It is not always clear what the mechanism is that is causing the problem. Is it hormones, low self-esteem, high self-esteem, hunger, lack of sleep, or just immaturity? And trying to discuss these problems with a teenager is like trying to tell some scientists that they may not be as scientific as they think they are. You are met with anger and resistance, name-calling, and such behavior as often seen in teenagers.
    The problem with bubbles in ice, is that if you have already made up your mind, then all you will ever find in your studies is how to make the facts fit your preconceived notions. Science always suffers when there is a lack of objectivity. What is a primary cause of lack of objectivity? I would guess that grant money is one of the problems, as money has a way of driving scientific objectivity out the window. Writing papers, and having peer review, would also drive out objectivity, as scientists require the approbation of their peers in order to get papers published and books written.
    Those people who founded the principles of modern science had, for the most part, one thing in common. They were all independently wealthy, and therefore not dependent on anyone else for how to think about problems. When science became a job, with an employer, objectivity was lost.

  51. I have much enjoyed Caleb Shore’s down to earth approach to what is clearly a taxing subject. I have also read and missed understanding much of the erudite discussion that has followed.
    One aspect that has occurred to me that no-one has mentioned is the effect of the lateral movement of ice in the ice caps. Am I right in believing that, in one way or another, the ice caps are all moving subject to gravity? Are they not behaving like glaciers, albeit in slower motion. Non movement of the ice, say in a perfect bowl will only give a record as long as it took to fill the bowl, after which time excess ice/snow will be blown off or fall over the edge of the bowl.
    These shearing movements through the ice field will happen at disparate rates and at disparate angles. These will lead to a mixing of the ice as well as setting up stresses that will rupture gas bubbles. Being more or less a plastic at the depths/pressures suggested, ice will flow around bubbles to reform them in different layers and travelling through different time slices. How can anyone be sure that the core samples follow a true time sequence?

  52. Tony Mach says:
    November 2, 2011 at 1:06 am
    [….]
    And by the way, what the heck is wrong with being respectful towards other cultures? Especially when you are from the White/Christian/European culture and the other culture has been the target of subjugation and/or extinction in the name of your culture?

    Being blindly “respectful” towards other cultures is wrong whenever it condomes inhumane conduct and unjustifiable discrimination against another culture, including what you call “the White/Christian/European culture ” For example, being “respectful” of the Aztec culture’s taking a Mayan princess, flaying her alive, donning her skin, and returning her in this manner to the her Mayan father and king may not be a cultural practice worthy of respect just because it did not come from what you describe as “the White/Christian/European culture” which forbade such practices. In other words, discrimination and bias can be justifiable when it seeks to curb inhumane acts, and blind respect towards cultural practices can often result in inhumane or other improper acts. The human condition improves by improving cultures, and not by blindly tolerating their worst practices.

  53. I had hoped that you were going to get into the distribution coefficient for CO2 ice phase/gas phase and losses of CO2 on the surfaces of the devices used for sampling. Alas, I’m dissappointed. The above factors would lead to underestimating CO2 concentrations in ice cores.

    In analytical chemistry, “spike and recovery” experiments are accepted prodedures to demonstrate a measurement methods accuracy. To my knowledge, no one has published any work on this re: ice core analysis. I think I know the answer why.

    Does anyone know of CO2 in ice core spike and recovery results, how about published distribution coefficients for CO2 in ice core conditions?

  54. Joe says:
    November 1, 2011 at 10:48 pm

    re the drilling and lab uncertainty – I can honestly say that I have not bothered to research into this. Primarily because, as a geotechnical engineer, I know that when we take a core sample from out of the ground at some depth, and bring it to the surface, we are effectively releasing pressure on that sample. Depending on the various properties of the material being retrieved, it could be affected in a number of ways. So, for example, in really simple terms, if we imagine a 3inch core of ice, it will have ice bubbles in it, but the surrounding ice lattice will be de-stressed (in 3 planes) as a result of being lifted out of its environment, and in addition, the ‘internal’ pressure from the bubbles should be higher than the pressure on the outside and thus trying to ‘exit’ the sample. (in geotechnical terms, we call this pore pressure)
    Compacted ice will have various planes of weakness through it (minute fault lines if you like as the ice crystals are forced together,etc) and hence, pressured gas from the bubbles could escape. However, it is not really possible for lower pressure atmospheric gas to enter the bubbles (at least not the ones in the middle of the sample). so the issue of accuracy is really only dependent on the quality of the ice core itself, the time in open low pressure air before bubble analysis, etc, and of course, the the care with which gas from bubbles is extracted.
    I must admit, I was watching some program on it once and they were cutting up ice cores into slices, which kind of bothered me, as that obviously allows for potential gas mixing through smaller ‘walls’ of ice around any bubbles but I am aware that there are several gas extraction techniques they have used which AFAIK are pretty good.

    This article highlights the uncertainty in the gas bubble formation – and whilst there are potential errors in any analysis – the main root of error/uncertainty must be in the actual ice bubble formation IMO?

  55. Sandy says:
    November 2, 2011 at 4:13 am

    So diffusion dominates compaction outflow, ok.
    Could the nuclear test of the 60′s be used as a marker to see how wide the diffusion is??
    ______________________________

    That is what made Dr. Jaworowski smell a dead rat.

    ….Dr. Jaworowski has devoted much of his professional life to the study of the composition of the atmosphere, as part of his work to understand the consequences of radioactive fallout from nuclear-weapons testing and nuclear reactor accidents. After taking numerous ice samples over the course of a dozen field trips to glaciers in six continents, and studying how contaminants travel through ice over time, he came to realize how fraught with error ice-core samples were in reconstructing the atmosphere. The Chernobyl accident, whose contaminants he studied in the 1990s in a Scandinavian glacier, provided the most illumination.

    “This ice contained extremely high radioactivity of cesium-137 from the Chernobyl fallout, more than a thousand times higher than that found in any glacier from nuclear-weapons fallout, and more than 100 times higher than found elsewhere from the Chernobyl fallout,” he explained. “This unique contamination of glacier ice revealed how particulate contaminants migrated, and also made sense of other discoveries I made during my other glacier expeditions. It convinced me that ice is not a closed system, suitable for an exact reconstruction of the composition of the past atmosphere.”

    http://www.nationalpost.com/news/story.html?id=25526754-e53a-4899-84af-5d9089a5dcb6&p=3

    This link is from the Bubbles Part one article.

  56. > I’ll make up my own Yankee jargon, and call the boundary between
    > firn and ice, “The Firnopause.”

    Firnopause is rather like the the gradient in ocean salinity known as a halocline; therefore it is sometimes referred to as the HidethedeCline.

  57. The fact that the ‘gas age’ and ‘ice age’ are not the same is well known and many ice core records give both ages. Despite the apparently haphazard way the gas moves around, ice cores from different parts of the world show a high degree of synchronicity.

    In some cases the difference between the ‘ice’ and ‘gas’ age can be hundreds of years. This means that the gas in the ‘little bubbles’ is a ‘weighted’ average over a period of centuries. A corrolory of this is that temperature increases such as those from 1910 to 1945 or 1975 to 2000 would not be picked up in the longer ice core records. From this it follows that it is not possible to know whether or not the temperature plateau of the last decade is unprecedented.

  58. JimBrock says:
    November 2, 2011 at 7:47 am

    I have wondered about this in another way. If CO2 can diffuse from the air bubble into surrounding ice, how much negative bias (CO2 concentration may be much lower than measured) is inherent in the process. I am confident that there have been some studies that consider this and offer corrections…can anyone give me a cite?
    _______________________________________
    The study was suggested and stomped on.

    (Starting from my last quote from the same artic/e)

    ….. It convinced me that ice is not a closed system, suitable for an exact reconstruction of the composition of the past atmosphere.”

    Because of the high importance of this realization, in 1994 Dr. Jaworowski, together with a team from the Norwegian Institute for Energy Technics, proposed a research project on the reliability of trace-gas determinations in the polar ice. The prospective sponsors of the research refused to fund it, claiming the research would be “immoral” if it served to undermine the foundations of climate research.

    The refusal did not come as a surprise. Several years earlier, in a peer-reviewed article published by the Norwegian Polar Institute, Dr. Jaworowski criticized the methods by which CO2 levels were ascertained from ice cores, and cast doubt on the global-warming hypothesis. The institute’s director, while agreeing to publish his article, also warned Dr. Jaworowski that “this is not the way one gets research projects.” Once published, the institute came under fire, especially since the report soon sold out and was reprinted. Said one prominent critic, “this paper puts the Norsk Polarinstitutt in disrepute.” Although none of the critics faulted Dr. Jaworowski’s science, the institute nevertheless fired him to maintain its access to funding…..

    http://www.nationalpost.com/news/story.html?id=25526754-e53a-4899-84af-5d9089a5dcb6&p=3

    This should come as no surprise to long time readers at WUWT. Climate Scientology is not and has never been anything but a political excuse used to extract more wealth from the general population and tighten the controls of government over people’s actions.

  59. D. Patterson says:
    November 2, 2011 at 8:28 am

    The references of the Law Dome ice cores I provided show that:
    – the air at closing depth is 7 years younger than the atmosphere.
    – the average distribution of air age in the firn and ice is about +/-5 years for the bulk of the gas.
    – there is no difference in CO2 levels between still open pores and already fully closed bubbles.
    – there is an overlap of 20 years between the gas in the ice core bubbles and the measurements at the South Pole, all data are within the accuracy of the CO2 measurements (1.2 ppmv – 1 sigma).

    From other references:
    – there are overlaps for increasing time periods between largely different ice cores for temperature, ice accumulation, salt/dust/bacterial inclusions,… which shows differences of maximum 5 ppmv for the same time periods.
    – a recent investigation of sediments shows roughly the same CO2 variability over a longer time frame (2 million years), independent of ice cores, be it with lower resolution.
    – migration plays a minor role in “warm”, coastal ice cores. That broadens the resolution after (ten)thousands of years, but doesn’t change the average over that time frame.
    – there is a very good, linear correlation between a temperature proxy (dD and D18O) and CO2 levels of ice cores. That shows that there is no CO2 migration in the coldest ice cores like Vostok and Dome C over 400-800 kyears.
    – there is a small migration at closing time and with conservation at elevated temperatures for the smallest molecules (oxygen, argon), not detected within the detection limits for CO2.

    All together, a lot of objections against ice cores were answered already in 1996 by Etheridge and later by others, some small problems were found later, but had little consequences for CO2 levels. It is impossible to give a 100% proof that ice core CO2 measurements are reliable. But all available evidence shows that they are, if performed with the best possible care. I haven’t seen any counterindications which were based on real data…

  60. Have you ever considered that there is no “direct” evidence as to the ages of the ice core samples? All ages attributed to the samples depend on assumptions (like ignoring C14 levels as irrelevant). And if the assumptions are incorrect, then your conclusions will be incorrect. There are other proposed models that have alternate explanations for what is found. All have the same “directly measured” data. The interpretation of the data depends on one’s faith in the assumptions upon which the model is based. You might even say that it is a “religious” disagreement, which might help you to understand why it is so difficult to convince a ‘true believer’.in anthropogenic global warming that the data they rely on does not support their ‘faith’.
    Ian

  61. Gail Combs says:
    November 2, 2011 at 9:35 am

    That is what made Dr. Jaworowski smell a dead rat.

    Gail, the migration of metal(ions) is completely different from CO2 or other molecules. CO2 doesn’t migrate through the ice matrix, while metal ions do.

  62. JDN says:
    November 2, 2011 at 8:10 am

    We have human artifacts with verifiable provenance in the ice from 40+ years ago. Can’t we just dig one of them up and measure the gas content of the ice right next to it? Hasn’t this been done? There’s also carbon dating to compare to ice gas content. I don’t understand why this is being treated as a purely theoretical issue, when experiment is clearly possible.
    ___________________________________

    Because it is not science it is propaganda or Lysenkoism. Read: The article: Zbigniew Jaworowski the ice core man

    http://www.nationalpost.com/news/story.html?id=25526754-e53a-4899-84af-5d9089a5dcb6&p=3

    And then his Paper: http://www.co2web.info/stoten92.pdf:

    More pdfs on Dr. Segalstad’s website: http://www.co2web.info/

    They have gotten away with the propaganda because unlike measuring temperature, measuring CO2 takes know how and expensive equipment. Also the fraud is not very easily spotted but it is there.

    Take a look at the assumptions put into measuring CO2 at Mauna Loa.

    At Mauna Loa we use the following data selection criteria…

    4. In keeping with the requirement that CO2 in background air should be steady, we apply a general “outlier rejection” step, in which we fit a curve to the preliminary daily means for each day calculated from the hours surviving step 1 and 2, and not including times with upslope winds. All hourly averages that are further than two standard deviations, calculated for every day, away from the fitted curve (“outliers”) are rejected. This step is iterated until no more rejections occur.

    Thanks to this “outlier rejection” step they reject something like 99+% of the data according to Zbigniew Jaworowski and Segalstad. (paper)

    You will also find the papers all include Keeling or one of his students. At this location:

    http://scrippsco2.ucsd.edu/data/atmospheric_co2.html

    something like 14, and practically all are publications by Keeling et al.

    Can you say Monopoly??? Keeling et al. are as bad or worse than the “Climategate Team” in their stranglehold on the “science”.

  63. One other point that most people miss. From my other reading someone floated the idea that education is “shaped” by giving scholarships to those of the “Correct mindset” This allows wealthy foundations like Carnegie, Ford, Rockefeller, Rhodes (Rothschild) to have a major input on the direction of education as a whole.

  64. RE: Tony Mach says:
    November 2, 2011 at 1:06 am

    Tweak……….gotcha!

    Actually that was a high-risk tweak, and I deleted it in one version, but your response makes me glad I left it in the final version.

    Do you have any idea how flagrantly disrespectful you are being towards Yankee culture, when you state, “And by the way, what the heck is wrong with being respectful towards other cultures? Especially when you are from the White/Christian/European culture and the other culture has been the target of subjugation and/or extinction in the name of your culture? ”

    Get ready to be seriously tweaked.

    When the Pilgrims dragged ashore in 1620 they were saved by sheer luck (or the Grace of God) because not only had the native population been 90-95% depopulated by a pandemic, but the winter they faced was amazingly mild and snow-free (especially for the Little Ice Age.) Even so many died. Less than 100 survived. But now look around America. How many people can (whether they know it or not) trace back in their family tree and discover they have a forefather who was aboard the Mayflower? An amazing 35 million. (In 2002) Roughly 10% of the population!

    Obviously they were winners. What happened to losers? Check out Battle of Lepanto in 1571. The Turkish fleet was galleys, side by side, stretching roughly two miles, numbering 300, with nearly 100 in reserve. What powered those ships? Who was chained to the oars, and went down screaming as the Turkish ships sank? Largely it was white, Christian losers.

    Sorry. That was the “entitlement” losers got, back in the old days. Some suggest it may have
    been the fate of the final Greenland Vikings: A ship appeared on the horizon, but the crew was not friendly. Greenlanders were herded aboard and sold as slaves (but at least were slaves where it was warmer, and likely were fed better.) (Columbus and Cabot may have heard of them, as young men in Italy, and for all we know the gossip of sea-dogs and wharf rats about Greenlanders may have prompted Columbus and Cabot to sail west in the late 1400’s.)

    The Pilgrims knew what happened to losers. Even while starving one of the first things they did was lug a cannon up a hill, and point it towards the sea. Not only did they fear Europeans, but also the fierce “Red Vikings,” a Micmac clan called the Tarenteen. Also Algonquin tribes knew what happened if they lost to the Iroquois, which is why they abandoned nearly all their settlements in Vermont before the Pilgrims landed.

    I’d rather be a winner. The Indians who lost to the Pilgrims were sold as slaves. Sad. But Yankees paid for that with the Civil War. Every New England graveyard has a stark reminder of the price the Yankee paid.

    So don’t lay any guilt trips on me. And don’t call me European. Do you see any Yankeeland in Europe? In Europe, when you have been rude and they say, “Yankee go home?” are they asking you to stay?

    Most Yankee are not even truly white. Besides the Mayflower in most family trees, you discover there is an old “family secret,” and most Yankee are between an eighth and a sixty-fourth “native.”

    And don’t think you are spiritual, when you rub the name of my people in the mud. I am proud to be a Yankee, and am going to tweak any Liberal who believes it is politically correct to be racist towards any people. (And if you don’t think this attitude steeps Climate Science, you have scales on your eyes.)

    In fact, if you don’t shape up, I’ll write a song, and treat you like Lynyrd Skynyrd treated Neil Young: http://www.youtube.com/watch?v=ye5BuYf8q4o&feature=related

    .

  65. Tony Mach says:
    November 2, 2011 at 1:06 am
    “Now, that was uncalled for, that scientists use their lingo to be “politically” correct. You could have come up with all kinds of reasons, but this is bullsh*t.”

    I find that last word in your sentence a tiny bit offensive, Tony.

  66. Excellent post

    Anyone ever freeze soda pop and then thaw it? Its pretty flat. That CO2 gets out even though its dissolved in the water.

    I do not see how the gasses would get forced into the ice in the first place either. It will want to migrate as the ice crystals set up. The water will expel it as the formation of ice causes great pressures on the surrounding molecules.

    IIRC, Ice relies on hydrogen bonds and cannot bond to gas molecules at all. This will enhance the migration of the gas molecules.

    This mechanism explains why the CO2 tends towards a uniform low limit.

    I wonder what the CO2 composition of just the water in a snowflake is?

    This should be easy to test.

  67. Caleb,

    A great post. A real dialogue opened up – the contributors contributed: I learned as much from your questions/confusion I shared with their answers as I did from your thoughts. And it was fun.

    Fun. Not politically incorrect, but, by Climate Wars respect, INTELLECTUALLY incorrect.

    Keep up the good speculating.

  68. bones says:
    November 1, 2011 at 9:06 pm
    “Although there might be some bulk flows associated with outflows from compaction and changes of barometric pressure, the exchanges of gases above the “firnopause” should be dominated by diffusion processes. For example, for CO2 in air at the freezing point of water, the diffusion coefficient is about 0.14 cm^2/s. In sixty years, CO2 molecules could move diffusively about 400 meters, which is about three times the depth to your firnopause. ”

    You forgot to include effects of porosity (90% near the top, but only about 10% open at lower levels), constrictivity (I don’t have a good guess for this but it is several times), and tortuosity (I would guess at least 3X). These would lower the EFFECTIVE diffusion coefficient by well more than 30 times at the lower level, and somewhat less higher up. Thus diffusion is probably smaller than 14 meters per 60 years as you go to lower levels, and pressure driven exchange dominates higher up, so mixing is significantly limited near the firn. There will be some smoothing of multi-years data, but closer to Caleb Shaw’s argument than you stated.

    The data for much slower closing of firn (where snow fall is far slower to accumulate) may have a larger gas mixing due to diffusion occurring over the much longer period, but we are examining the Greenland case here.

  69. Sorry, I had a lot of work today and can’t read all comments atm.

    But what came into my mind today, while thinking about the ice cores:

    Imagine what an uproar science would experience, if the alarmists’ one-and-only CO2 proxy for pre-industrial CO2 would fall apart of wrong ice core data!
    How many thousands of peer-reviewed and published papers from renowned journals would be afflicted? How many papers were afflicted that were build upon wrong predecessors?
    This would turn all science upside down!

    Phew… better not develop thoughts further.

  70. Gail Combs says:
    November 2, 2011 at 10:20 am

    measuring CO2 takes know how and expensive equipment

    For 149 euro you can buy one with sufficient accuracy to show how much CO2 you are exhaling inside your home:

    http://www2.conrad.be/goto.php?artikel=102541

    Just read the display… Not very accurate (+/- 75 ppmv), but still better than some historical measurements…

    Thanks to this “outlier rejection” step they reject something like 99+% of the data according to Zbigniew Jaworowski and Segalstad.

    If that is really what they said, then they are telling nonsense. You can download the uncorrected, raw hourly data from Mauna Loa yourself at:
    ftp://ftp.cmdl.noaa.gov/ccg/co2/in-situ/

    I have done that for the year 2004:
    8784 hourly average data should have been sampled, but:
    1102 have no data, due to instrumental errors (including several weeks in June).
    1085 were flagged, due to upslope diurnal winds (which have lower values), not used in daily, monthly and yearly averages.
    655 had large variability within one hour, were flagged, but still are used in the official averages.
    866 had large hour-by-hour variability > 0.25 ppmv, were flagged and not used.

    Thus in total 75% of the available data were used. But even if you include or exclude the outliers, that doesn’t make one damn difference for the trend or the yearly average. It is because Keeling and his successors want to present background data, not what is incfluenced by volcanic vents or vegetation from the valley. If you want to know that kind of data, simply measure near the vents or near/inside the vegetation…

    See the difference between “all” data and the “selected” data:

    and

    Thus again, you are refering to Jaworowski/Segalstad, without checking in how far what they say is true. A little more skepticism against (some) skeptics might be healthy…

    Further the modern rules for not using outliers (but still available online!) for averaging and trends are strictly fixed before the facts, as we may expect from real scientists:

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

  71. #
    #
    Ferdinand Engelbeen says:
    November 2, 2011 at 10:02 am

    Gail Combs says:
    November 2, 2011 at 9:35 am

    That is what made Dr. Jaworowski smell a dead rat.

    Gail, the migration of metal(ions) is completely different from CO2 or other molecules. CO2 doesn’t migrate through the ice matrix, while metal ions do.
    _____________________
    Your argument is
    #1 No liquid phase occurs within the ice.
    #2 The process is entirely mechanical with no chemical or physical processes.

    This (#1 + 2) is invalid because liquid phases were found within the ice in Antarctic at even the lowest temperature. It was found there were capillary like interstital voids filled with brine, melt, cabonates, in early studies. They also found there was mobility of CO2 within the ice. Later studies ignored these findings because they did not “FIT” the story line.

    In a plastic bottle soda will go “Flat” within a year or so because plastics are so porous. Even glass has a problem with migration although it is slower. Ice is a heck of a lot more “Polar” than plastic and has an affinity for CO2.

    The idea that the gases do not “Migrate” is idiotic. You have a crystal lattice with pores and water/brine AND tremendous pressure, sounds like a gas chromatograph to me. And any one who has worked with gas or liquid chromatography is very aware of differential migration of different molecules because of differences in the polarity of the molecule.

  72. Caleb

    Your post at 10.39 raiseed three extraordinary coincidences, two over in my own thread here;

    http://wattsupwiththat.com/2011/11/01/a-short-anthology-of-changing-climate/

    Firstly, I also mention the Mayflower experience here;

    “However, that mild conditions can prevail even during the harshest periods of the LIA can also be seen here, when we examine the arrival of the Mayflower in America in 1620. The initial cold weather quickly gave way to a mild winter described here;

    http://www.stormfax.com/thanksgv.htm

    “The winter of 1620-’21 was “a calm winter, such as was never seen here since,” wrote Thomas Dudley of Massachusetts Bay in 1630. Edward Winslow, one of the original Pilgrims, also wrote about the “remarkable mildness” of that first winter in Good Newes from New England, published in 1624. There was testimony by others to a mild end of December, a moderate January, a brief cold spell with sleet and some snow in early February, followed by definitely mild conditions and an early spring.”

    Secondly, your reference to Christian slaves is mentioned within this link here; (White Christian Slaves were taken from the shores of the beach I look out on in Southern England and the Church I also overlook took collections in order to raise money to free them)

    “In this next article the author looked at the lives and times of famous people living in Teignmouth on the South Coast of England in order to examine the warming trend-punctuated by cold periods- experienced in Europe through the 19th Century by following one of this town’s famous sons-the harpist Elias Parish Alvars- as he travels through Europe on concert tours.

    http://noconsensus.wordpress.com/2010/02/06/travels-in-Europe-part-1/

    Third coincidence is that I was standing on the Mayflower steps in Plymouth just a couple of days ago

    All the best
    tonyb

  73. petermue says:

    Imagine what an uproar science would experience, if the alarmists’ one-and-only CO2 proxy for pre-industrial CO2 would fall apart of wrong ice core data!

    Don’t you think that if the ice core data were really wrong/falsified, at least one of the hundreds of persons in a lot of different organisations of different countries involved in ice core research would bring that out, especially after retirement…

  74. Ferdinand

    If I bought one of the cheap 149 Euro devices you mention, would I be able to stand on the beach close to my house and see any discernible difference in co2 levels between winter (water temp around 6degres C) and summer (water temperature if we are lucky 20 degrees C).

    In other words at what temperature point does water change from being a sink to a source?

    Ps Please answer quickly so I can use my Euros up before they are replaced by a more sensible currency-such as sterling :)
    tonyb

  75. Is ice actually hermetically sealed with respect to air? Water isn’t. So we’re sure that ice is?

  76. Gail Combs says:
    November 2, 2011 at 12:58 pm

    Your argument is
    #1 No liquid phase occurs within the ice.
    #2 The process is entirely mechanical with no chemical or physical processes.

    In pure ice, there is no liquid water at the ice-air border below -32°C. Even at -20°C, the liquid-like layer is only 5 atoms thick. You can’t skate on ice below -20°C… And I don’t think that
    much CO2 can hide there. The ice between two crystals is more unordered than in the crystal, but still not liquid. Again hardly possible for CO2 to hide or migrate there.

    Only if dust, salts and/or bacteria are present, some (more) liquid may be present. That is more at coastal Antarctic ice cores than far inland. But there is hardly any difference between CO2 levels from coastal ice cores and inland ice cores in Antarctica, thus that plays little role.

    Dust, salts and bacteria can influence the CO2 levels. That is hardly the case for inland Antarctic ice cores, but potentially may play a role in coastal cores and for Greenland cores. The coastal ice cores have carbonate salts present which may give some 70-80 ppmv extra CO2 with addition of an acid. These are not present in the Antarctic, but they are occasionally present in Greenland, when nearby Icelandic volcanoes deposit their highly acid dust on Greenland’s ice…

    That is the reason why the Greenland ice core CO2 levels are unreliable, due to extra in situ CO2 production…

  77. Gail Combs says:
    November 2, 2011 at 12:58 pm

    Forgot to add:

    The idea that the gases do not “Migrate” is idiotic. You have a crystal lattice with pores and water/brine AND tremendous pressure

    What is the difference in pressure between ice at 2000 m depth and 2000.1 m depth and how much migration does that induce? And how many still open pores are left at that static pressure? Even the bubbles did disappear…

  78. Engelbeen says:
    November 2, 2011 at 12:52 pm

    Gail Combs says:
    November 2, 2011 at 10:20 am
    measuring CO2 takes know how and expensive equipment
    ———————————
    For 149 euro you can buy one with sufficient accuracy to show how much CO2 you are exhaling inside your home:

    http://www2.conrad.be/goto.php?artikel=102541

    Just read the display… Not very accurate (+/- 75 ppmv), but still better than some historical measurements…

    >>>>>>>>>>>>>>>>>>>>>>>>>>>>>
    As I said you need expensive equipment not draeger tubes. And yes I know what they are and have used them. They are not of much use they are nothing more than a “toy” in this application.
    >>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>

    Thanks to this “outlier rejection” step they reject something like 99+% of the data according to Zbigniew Jaworowski and Segalstad.
    ——————————————————
    If that is really what they said, then they are telling nonsense. You can download the uncorrected, raw hourly data from Mauna Loa yourself at:
    ftp://ftp.cmdl.noaa.gov/ccg/co2/in-situ/

    >>>>>>>>>>>>>>>>>>>>>>>>>>>>>>
    Here is the exact quote from J & S citing papers by Keeling and Bacastow.
    ….and the fact that the results of the measurements were “edited” (Bacastow et al., 1985); large portions of raw data were rejected, leaving just a small fraction of the raw data subjected to averaging techniques (Pales & Keeling, 1965). http://www.co2web.info/ESEF3VO2.pdf

    This is the SAME bait and switch we see with the “Raw Temperature Data”
    To again quoted from Mauna Loa Observatory.
    “At Mauna Loa we use the following data selection criteria:
    1.The standard deviation of minute averages should be less than 0.30 ppm within a given hour. A standard deviation larger than 0.30 ppm is indicated by a “V” flag in the hourly data file, and by the red color in Figure 2.
    2.The hourly average should differ from the preceding hour by less than 0.25 ppm. A larger hour-to-hour change is indicated by a “D” flag in the hourly data file….

    Sorry the HOURLY data and even the minute data are AVERAGES. Spikes get leveled. And yes they NOW make the “Raw” (averaged) data available.

    An Assumption was made that a “Background” CO2 exists and all the methods and data is geared to that assumption. This assumption was made by Callendar
    sixty years ago and was continued by Keeling and everyone else. This “Assumption” allows editing of data and the rejection of “Outliers”

    Sorry, I got my rear handed to me for rejecting outliers without a PROVEN D…M good reason. It was always a real big no no in the labs where I worked. That is IF the labs were run by honest people.

  79. climatereason says:
    November 2, 2011 at 1:07 pm

    If I bought one of the cheap 149 Euro devices you mention, would I be able to stand on the beach close to my house and see any discernible difference in co2 levels between winter (water temp around 6degres C) and summer (water temperature if we are lucky 20 degrees C).

    Hi Tony,

    Looking at the technical specs, the resolution is 1 ppmv, that is quite good and sufficient for your purpose. The absolute value may be between +/- 75 ppmv around the real value (there is some possibility to calibrate it with a calibration gas of known composition), but you can measure the differences between summer and winter, which is 6-8 ppmv up and down in our NH mid-latitudes. You can also measure the increase over the years of about 2 ppmv per year…

    The only point is that the CO2 exchange rate of the oceans with the atmosphere is low. Thus even a fastocean temperature change will give a slow response in release or absorption. The changes in vegetation are much faster and mixing speed of CO2 over the globe is faster too. Thus what you measure (even with wind only from the seaside) is more influenced by land vegetation than by seawater temperature…

  80. Gail Combs

    Thanks for sharing relevant (and IMO truly scientific) knowledge in spades.

    Having investigated the matter carefully, I am still sure, and will keep on saying, that the Ice Hockey Stick is the biggest neglected climate science scam.

    So I’m glad you drew attention to Segalstad and Jaworowski’s paper “Do glaciers tell a true atmospheric CO2 story?” Written before Jaworowski was confronting the growing science corruptions, it is very good on the pure science without the distractions of righteous indignation. I think it is as still good a paper on ice core science as one can find. I mistrust those “debunking” Jaworowski and suspect vested interests, with the exception of F Engelbeen.

    I retyped the whole paper and, with Segalstad’s blessing, uploaded it to my website, with a short introduction and a short codicil which addresses Engelbeen’s take. After finding several points at which I could not agree with FE and found him referencing the inflammatory “Some Are Boojums” to debunk Jaworowski, I tired of further pursuit of refutation. Shame. I like FE.

  81. Above I said

    An Assumption was made that a “Background” CO2 exists and all the methods and data is geared to that assumption. This assumption was made by Callendar
    sixty years ago and was continued by Keeling and everyone else. This “Assumption” allows editing of data and the rejection of “Outliers”

    There are actually two assumptions.
    The atmosphere is “well mixed” and that leads to the second assumption that there is a “background” CO2 level.
    The problem is the assumptions is leads to circular reasoning. There is a background CO2 level of “380” ppm, because I “Know” that I then reject a reading of 248 ppm and a reading of 573 ppm because obviously they can not be the “background” level in a well mixed atmosphere.

    As Ferdinand Engelbeen has amply illustrated, anyone who challenges those assumptions is called into question.

    Jaworowski, Segalstad and Beck have shown older data for atmospheric and Ice Core CO2 was higher and more wide spread than that “allowed” to be published today. Any challenge to the established dogma is met with the full force of peer pressure up to and including firing.

    Now the JAXA satellite data has turned the whole CO2 emitted by evil mankind destroys mother Earth on its head.
    Map: http://www.jaxa.jp/projects/sat/gosat/img/topics_20111028.jpg
    Secondary map: http://www.suite101.com/view_image_articles.cfm/3499100
    Japan Aerospace Exploration Agency: http://www.jaxa.jp/projects/sat/gosat/index_e.html

    CheifIO has a clear picture in his article.: http://chiefio.wordpress.com/2011/10/31/japanese-satellites-say-3rd-world-owes-co2-reparations-to-the-west/

  82. old44 says:
    November 1, 2011 at 9:08 pm
    Is Caleb Shaw Douglas Adams?

    Not unless he’s ghost writing. Literally.

    Douglas Adams, 1952-2001, RIP

  83. Gail Combs says:
    November 2, 2011 at 2:31 pm

    As I said you need expensive equipment not draeger tubes.

    As explained to Tony, the apparatus has a resolution of 1 ppmv. It is a continuous measuring device, equiped with a relay to set of an alarm or to start air exchanges. The measurement principle (NDIR) is the same as at Mauna Loa…

    large portions of raw data were rejected, leaving just a small fraction of the raw data subjected to averaging techniques

    75% of the data were retained, a little more than the 1% you mentioned. But the main point is that the rejection of the outliers doesn’t influence the average or the trend, only the trend looks better without the outliers… And it is the trend which is of importance, not the volcanic plumes or the vegetation at Hawaii…

    Sorry the HOURLY data and even the minute data are AVERAGES. Spikes get leveled. And yes they NOW make the “Raw” (averaged) data available.

    In the old days of Keeling, the raw voltage data were plotted on long paper rolls, which means a lot of work to collect and calculate the CO2 levels from the calibration data and the sample data. Since 1974 the data are collected by a computer system. As described by Pieter Tans of Mauna Loa, the system collects 2×20 minutes of 10-second sample snapshots (raw voltage) from two intake lines followed by three calibration gases which are sampled too at 10-second intervals for several minutes. The 10-second voltage readings are not on-line but on simple request (to Pieter Tans) supplied if you want to control the calculation of the CO2 levels, which is what I have done.

    The 2×20 minutes sampling is averaged and presented on line as average for that hour, but as the standarddeviation of the sampling is given too, that shows how much variability there was in the past hour. Thus if you don’t agree to reject any outlier, you are free to include all data, including a 3 sigma error band… It doesn’t matter, because that doesn’t change the trend at all…

    At last, I still wonder why some skeptics are allergic for stringent criteria for outliers in some cases and insist on rejecting in other cases:
    In the case of Mauna Loa, it is proven that a high variability within one hour is caused by nearby volcanic vents. These data have nothing to do with the data one is interested in, thus are rightfully rejected. The same for upslope wind, depleted due to local vegetation.

    In the case of temperature data, a lot of people rightfully ask for rejecting of data taken from asphalted parking lots etc… In that case there is an influence on the trend. But even if there wasn’t, we aren’t interested in the temperature of asphalt or its trend over the years…

  84. D. J. Hawkins says:
    November 2, 2011 at 3:34 pm

    old44 says:
    November 1, 2011 at 9:08 pm
    Is Caleb Shaw Douglas Adams?

    Not unless he’s ghost writing. Literally.
    Douglas Adams, 1952-2001, RIP

    What Hotblack Desiato can do, Douglas can.

  85. Steven Kopits says:
    November 2, 2011 at 1:24 pm

    Is ice actually hermetically sealed with respect to air? Water isn’t. So we’re sure that ice is?

    Sorry, but there is a lot of (frequently repeated every now and then) discussion between who believes in what Jaworowski/Segalstad say and who don’t. That makes that simple questions like yours are more or less neglected.

    What Etheridge e.a. (1996) have done is measuring the CO2 levels in firn and ice at closing depth. That shows that there is no last-minute migration out of the bubbles when these are closing. Then there is an overlap of about 20 years between the data in the ice cores and the direct measurements at the South Pole. Thus even with increasing pressure, there is no measurable migration out of the ice over a period of 20 years. That is pretty short to make any conclusions for the long-term (back to 800,000 years) rate of migration.

    There was some laboratory test, mimicking the Vostok ice core pressure and temperature, but that didn’t give usable results. The main problem is that if there is migration, the speed is so slow that it is near impossible to measure that in laboratory circumstances.

    There were theoretical calculations, based on CO2 migration nearby remelted layers in the Siple Dome ice core. Based on these calculations, there is some migration at medium depth, which makes that the averaging broadens from 20 to 22 jears and at full depth (70 kyr old) from 20 to 40 years.

    And last but not least, there is a quite good linear ratio between CO2 levels and temperature (proxies) in the Vostok and Dome C ice cores over 800,000 years. If there was the slightest migration, the ratio would fade over time…

    Thus all together, there are a few indications that there is little migration in “warm”, coastal, ice cores but no indication at all for migration in “cold”, inland ice cores… Thus one can say that air is hermetically sealed in ice if the temperature is low enough…

  86. It would seem to me that atmospheric pressure changes would make the snow or “firn” breath in and out 10% of its air volume each change cycle. Seems to me that this would result in mixing. The firn closest to the Firnopause would breath out 10% of its air, then breath in the 10% of air back, but now it is mixed with higher up air, 10% of which would be air it just breathed out (1%). That seems to be quite efficient mixing. So I would tend to agree that the 1951 air is no longer present. However, as the firn gets lower and lower, there would be less and less mixing. I would think that the air bubble would have air from every year from say 20 years after the snow fell (1971) all the way until the Firnopause. I would imagine it would have very little air from 2011, but likely 1 or 2 molecules. Some year that I can only guess at would have more than any other year. I would guess 1996.

  87. Ferdinand Englebeen;
    Don’t you think that if the ice core data were really wrong/falsified, at least one of the hundreds of persons in a lot of different organisations of different countries involved in ice core research would bring that out, especially after retirement…>>>>

    Sorry Ferdinand, but that comment just ticks me off. A lot of what you said in other comments has merit, though I disagree with some of your points. But that statement is just pure garbage. Lots of people have questioned the accuracy of ice core data, but the fact of the matter is that the people who have extracted the ice cores and extracted data from them don’t exactly number in the tens of thousands. The bulk of them are involved in processes that they believe in, and being small (comparitively) in numbers, the opportunity for confirmation bias is substantial. Its not like we have multiple groups like UAH, RSS, GISS and HadCrut competing to uncover each others errors and improve the accuracy of their own work, is it? In fact, given the huge number of errors those groups have had exposed in their work over the years, how is it that ice core data hasn’t experience the same?

    Further, how does one “prove” the ice cores wrong? You say they match actual measurements at the south pole. So what? For how many years? Have you forgotten the various tree ring and other proxy data that were presumed to match actual measurements world wide…until the quit doing so a few decades ago? How do you know that the same convergence/divergence isn’t at play for the VERY short time period you have to compare actual measurements against ice core data?

    FURTHER, the only other data we have older than a few decades is in fact the measurements taken by many scientists over the years and compiled in various ways by Beck and his colleagues. The fact that the ice core data doesn’t match means that one, or both, are wrong. To “prove” one right, you need a tie breaker, and there simply isn’t another proxy that I am aware of to be that tie breaker.

    That said, Beck’s data shows a steep decline in CO2 at the time that tree rings began diverging from the temperature record. There being no other explanation for the tree ring divergence problem, does that not strike you as evidence worthy of additional investigation and consideration?

    Defend your science with facts, and I will listen attentively to every word you say. Rely on arguments like well, no one has come clean, not even the retired ones, and you cast yourself amongst those who argue from authority and have no real science to rely on. I’ve read enough of your writing to know that isn’t true of you, but you do yourself a disservice by arguing from that perspective.

  88. FE: “You can’t skate on ice below -20°C”
    I can’t skate on ice above -20 C either, but that was due to balance, not temperature, as my ruddy faced compatriots all too gleefully pointed out.

  89. Ferdinand Engelbeen says:

    The reference you gave only shows that the resolution of the ice core (the averaging over a period) theoretically broadens from 20 years to 22 years at some depth to 40 years at full depth (at 70 kyr age).

    Yes, that’s the main gist, but they present data that makes me go Hmmm.

    For example, look at their figure 3

    http://www.geocraft.com/WVFossils/Reference_Docs/CO2_diffusion_in_polar_ice_2008.pdf

    @ 286.74m it’s 325 ppm CO2 then @ 286.77m it’s 700 ppm CO2.

    According to:

    http://soap.siteturbine.com/faculty/faculty_files/publications/1086/avk815.pdf

    The annual layer thickness @ that depth is about 6 cm, give or take. So basically in a year CO2 went from 325 to 700 ppm as recorded in the ice.

    Hmmm. If you go by what they say: “Refrozen melt layers in the Siple Dome ice core contain
    excess CO2 due to the high solubility of CO2 in the meltwater.” …. “Assuming an atmospheric CO2 concentration of 278 ppm (matm/atm) (Indermu¨hle and others, 1999) at the gas age of 2.74 kyr BP and surface pressure at Siple Dome of 937 hPa, we expect 16 230 ppm CO2 (umol CO2 /mol total air) dissolved in 0°C meltwater in equilibrium, 58 times greater than in the atmosphere (Table 1).” And cite “Pilson (1998)” in Table 1’s text for the 16230 ppm CO2.

    WHAT!?

    Ok let’s start with Pilson (1998), the name of the book is “Introduction to the Chemistry of the Sea”. Ok, so what does that have to do with snow (that’s what it was before it melted) that fell 130 km away from the ocean @ some 400 meters above sea level?

    Ok, how about that high solubility: Nope, solubility of CO2 in water is less than 4 ppm.

    http://www.engineeringtoolbox.com/gases-solubility-water-d_1148.html

    Ok, how about that 16,230 ppm. (umol CO2 /mol total air).
    I know it’s been a long time but isn’t that like 24k ppm(mg/kg)? How? Why?

    Ok, moving on to that “58 times greater than the atmosphere”? I’ve never seen that ratio before. Why don’t we all just put some meltwater outside and suck the CO2 out of the atmosphere?

    Again,
    Where did the excess CO2 come from?

    Why is Beck a crank (because his variability is impossible) for proposing less variability than this ice core data?

  90. John West says:
    November 2, 2011 at 11:23 pm

    “we expect 16 230 ppm CO2 (umol CO2 /mol total air) dissolved in 0°C meltwater in equilibrium, 58 times greater than in the atmosphere (Table 1)”

    The coastal ice cores contain quite an amount of salts (ordinary salt, but also carbonates) blown in from the sea (as salt spray). The carbonates form a buffer which increases the solubility of gaseous CO2 tremendously (seawater does dissolve enormous quantities of CO2, compared to fresh water).
    As long as there is no remelt, that doesn’t matter much, as there is little migration and the CO2 measurements are done under vacuum, effectively pulling out all available free CO2 out of any liquid layer at the surface of the bubbles (except if some acid dust is deposited, which increases the free CO2 content, as is the case for Greenland ice cores).
    If there is remelt, that concentrates the high CO2 solution downward until a impermeable layer is barring the path. After refreezing, there you will find much higher CO2 levels in the bubbles… The same happened to the Xe/Ar and Kr/Ar ratio’s: xenon and krypton both are more soluble in water than argon, thus any percolation of water through the firn will increase the Xe/Ar and Kr/Ar ratio.

    This mechanism was used to calculate the migration of CO2 through the ice core, because the expected amount of CO2 in around the refrozen ice differed from what was found. Even so, this is a pure theoretical calculation of the migration speed, which needs validation, which is hard to obtain.

    The increased CO2 near remelt layers is a concentration of CO2 from many younger years into a small part of the ice core. Even that doesn’t change the average, because CO2 was removed from other layers above it. In contrast, the figures supplied by the late Ernst Beck are based on local snapshots mostly at places which show huge hourly variations in CO2 level.

    You can compare Beck’s result to taking a few years temperature measurements in rural Finland and combine that with a few years measurements in the middle of Rome on a hot asphalt roof and again with a few years from rural Siberia. And then conclude from the trend that the middle years were much hotter…

  91. Robert Clemenzi says:
    November 2, 2011 at 9:36 pm

    CO2 is not correlated with either. You should plot the data yourself.

    Which is what I have done:

    The trend gets even better if you compensate for the 800 yr lag during a glacial-interglacial transition and a few thousand years during an interglacial-glacial transition…

  92. I’d like to again thank all the people who commented. I can see I was in error when I failed to consider the diffusion of gasses.

    I am not helped much by mathamatic explainations such as: http://en.wikipedia.org/wiki/Diffusion_equation
    However I am helped when someone simply asks me to consider how I can smell a drop of perfume so soon, when it is spilled on the far side of a room with still air.

    I still am curious about how freely gas actually moves through the firn. If I had grant money, I’d like to place barometers at various levels from top to bottom, and then reseal the bore holes. Also, after looking both ways to make sure no rabid environmentalists were nearby, I’d like to set up an array of geiger counters and then release radon gas just above the “firnopause.” Any upward movement of the radon at all, unexplained by diffusion, would suggest older gas was being squeezed upwards, and the “little bubbles” held gas older than expected.

    The path of gas to the surface is not a straight line, and is longer than some think. (The coast of Maine is longer than the coast of California.)

    Thanks again to all.

  93. Ferdinand:

    Please try to keep within the bounds of reality. At November 2, 2011 at 10:02 am you assert:

    “Gail, the migration of metal(ions) is completely different from CO2 or other molecules. CO2 doesn’t migrate through the ice matrix, while metal ions do.”

    No! Absolutely not! You know that is a falsehood.

    As I have repeatedly explained to you. For example, at November 1, 2011 at 3:04 am on the ‘Part 1’ thread I cited you having posted:

    “- He alludes that CO2 is migrating out of the bubbles during storage. But we measure 180-300 ppmv in the bubbles while the outside world is at 390 ppmv. That simply is physically impossible.”

    and I refuted that writing:

    “Your claim of “physically impossible” demonstrates your willful ignorance. Surfaces of ice and ice crystals are coated in a liquid phase (i.e. water) at all temperatures down to -40 deg. C (incidentally, this is why ice is slippery). And CO2 dissolves in water. So, CO2 certainly will migrate out of bubbles: it will dissolve and then experience ionic diffusion through the intergranular (i.e. between crystal) zones.

    Simply, your assertion that the bubbles trap the CO2 is an assertion of a physical impossibility (and I have good reason to suspect that you know it is).”

    You do not convert a falsehood into truth by repeating it.

    Richard

  94. davidmhoffer says:
    November 2, 2011 at 6:05 pm

    Ice core measurements are done in different laboratories, in France, England, the US, Japan,… Although the groups are not that big, there is a healthy competition between them, as good as there is between Scripps and NOAA for independent CO2 measurements at Mauna Loa and other stations (especially since Scripps lost their monopoly for calibration gases to NOAA). I am pretty sure that if there were errors in one of them, the other organisation would be happy to point that out…

    But, indeed that is not the main reason to defend the reliability of ice cores or CO2 measurements in the atmosphere. The reason I did use that argument is that some skeptics are so sure that the ice core data (and Mauna Loa data) are wrong, that there must be manipulation of the figures by all groups involved…

    FURTHER, the only other data we have older than a few decades is in fact the measurements taken by many scientists over the years and compiled in various ways by Beck and his colleagues. The fact that the ice core data doesn’t match means that one, or both, are wrong. To “prove” one right, you need a tie breaker, and there simply isn’t another proxy that I am aware of to be that tie breaker.

    First, the historical data match the ice core data, if only the data taken over the oceans and coastal with wind from the seaside are used. We know from current measurements that only the data taken over the oceans (or above 500 meters over land) are stable enough to be used as “background”. Unfortunately, there are no seaside data in Beck’s compilation for the period 1935-1955, thus there is no background confirmation for the period where Beck’s 1942 “peak” is.

    At this moment there are three tie breakers and the physical impossibility:

    – a brand new report about sediments shows that the ice cores are right and expand that to over 2 million years, independent of calibration against ice cores, be it with an even worse resolution over that long time span. Need to recover the reference, it was discussed some time ago here on WUWT.
    – stomata data are often used to show that the ice core data are wrong, but they suffer from the same problems as many of the historical data: they measure surface CO2 over land, which is highly variable not only hour by hour but also over history. The stomata data are calibrated for the period over the past century against direct measurement since 1960 and against… ice cores for the period 1900-1960. If there was a huge (80 ppmv!) peak around 1942, that would give an enormous sink in stomata index around that period, completely outside the range of the other data. But nothing abnormal is visible in the data series:

    1940 is around 310 ppmv in that graph.
    – coralline sponges give the 13C/12C ratio for over 600 years, with a resolution of 2-4 years. Although not a direct indication of CO2 levels, they show where any peak CO2 originated. If the peak was from the oceans or volcanoes, that would lead to an increase of the 13C/12C ratio. If the increase was from vegetation decay/burning, that would lead to a firm decrease of the 13C/12C ratio. But nothing special is visible in the 13C/12C ratio around 1942, only a steady decline in ratio to burning of fossil fuels:

    Last but not least, the physical impossibility:
    – an increase of 80 ppmv in only 7 years is not impossible, but highly implausible: that is the equivalent of burning down 1/3rd of all land vegetation on earth… That didn’t happen. Neither the sudden outbreak of thousands of volcanoes in a short period. Neither a sudden warming of the oceans with 10°C. The only possibility is a sudden acidification of the ocean surface (by what?).
    – the opposite movement of absorbing 80 ppmv in only 7 years time simply is impossible. There is no known mechanism on earth that can do that. Absorption rates of the oceans (even if there would be a sudden increase in alkalinity) is much too slow. The same for extra growth in vegetation. The current total net absorption of vegetation + oceans with the extra 100 ppmv CO2 pressure is not more than 2 ppmv/year…

    Thus in my informed opinion, the 1942 “peak” in the historical data is completely spurious.

  95. Lucy Skywalker says:
    November 2, 2011 at 3:03 pm

    Hi Lucy, some time ago since we did met…

    I don’t have any objection against Jaworoski as person, and I hope that his heath is improving. But he says things which are physicaly impossible, like the migration of CO2 from low levels to high levels. And he still insists that there is no difference in ice age and gas age of ice cores, while that was measured by Etheridge already in 1996 and confirmed in many more measurements in firn. Even if “some are bojums” is written by the enemy, that doesn’t imply that what they write is wrong. If Jaworowski writes that water was found at the ice crystal borders (implying that CO2 can escape), according to a certain report, but the report is not about water but about isolated suphuric acid islands, then Jaworowski is wrong and the enemy is right…

    Maybe he is right on other items, but I can’t trust him on his words without independent confirmation by others…

    Best regards,

    Ferdinand

  96. Ferdinand:

    To be clear to others, I respect your work and your sincerity. Indeed, I often – and again here – commend your web site as a source of CO2 information for all who need it.

    But, as you know, I am certain that you are grossly mistaken in your interpretation of much data. I am absolutely certain you are completely wrong in your trust of the ice core data and the importance of ‘background’ CO2.

    You disagree with Beck’s data because it has high variability, but that variability is its most important indication.

    At many localities the atmospheric CO2 concentration varies by hundreds of ppm between day and night. This indicates that local CO2 sequestration can easily absorb all the natural and anthropogenic emission in that locality. So, when considering an anthropogenic contribution to atmospheric CO2 concentration one needs to explain why the local sequestrations do not dominate. Indeed, the seasonal variations also indicate that local sequestration can easily cope with all the natural and anthropogenic emission.

    Therefore, the assumption that recent rise in atmospheric CO2 concentration (e.g. as measured at Mauna Loa since 1958) is a result of about half the anthropogenic emission accumulating IS FALSIFIED by the observations of local variability at all measurement sites.

    Furthermore, the radiative greenhouse effect results from actual concentrations of GHGs in the atmosphere and not some hypothetical ‘background’ concentration. If the CO2 concentration is high by day and low by night then that has a direct effect on the magnitude of any putative radiative greenhouse effect.

    The ice core data show falsely low variability in atmospheric CO2 concentration. Real measurements such as those collated by Beck provide much more useful information.

    Richard

  97. Ferdinand Engelbeen
    November 3, 2011 at 3:33 am

    @Lucy Skywalker you said,

    “I don’t have any objection against Jaworoski as person, and I hope that his heath is improving. But he says things which are physicaly impossible, like the migration of CO2 from low levels to high levels. [ . . . ] ”

    ———————–

    Ferdinand Engelbeen,

    You are so familiar to me on many open blogs who welcome open skeptical climate science discussion that when I see the words ‘Ice Core’ I start to subconsciously anticipate you. I always read discourses on ice cores because there is so much to consider when discussing the validity of any paleo climate parameter as such.

    Request – Based on your about quote could you please give me references to exact passages in the talks or papers of Prof Jaworowski where you think he says there is “migration of CO2 from low levels to high levels.”?

    Thank you.

    John

  98. It is advisable to remember a few facts:
    CO2 follows temperature, not the other way. Open a coke and you´ll see it: The more you have it in your warm hand the more gas will go out when you open it.
    CO2 is the transparent gas we all exhale (SOOT is black=Carbon dust) and plants breath with delight, to give us back what they exhale instead= Oxygen we breath in.
    CO2 is a TRACE GAS in the atmosphere, it is the 0.038% of it.
    There is no such a thing as “greenhouse effect”, “greenhouse gases are gases IN a greenhouse”, where heated gases are trapped and relatively isolated not to lose its heat so rapidly. If greenhouse effect were to be true, as Svante Arrhenius figured it out: CO2 “like the window panes in a greenhouse”, but…the trouble is that those panes would be only 3.8 panes out of 10000, there would be 9996.2 HOLES.
    See:

    CO2 is a gas essential to life. All carbohydrates are made of it. The sugar you eat, the bread you have eaten in your breakfast this morning, even the jeans you wear (these are made from 100% cotton, a polymer of glucose, made of CO2…you didn´t know it, did you?)
    You and I, we are made of CARBON and WATER.
    CO2 is heavier than Air, so it can not go up, up and away to cover the earth.
    The atmosphere, the air can not hold heat, its volumetric heat capacity, per cubic cemtimeter is 0.00192 joules, while water is 4.186, i.e., 3227 times.
    This is the reason why people used hot water bottles to warm their feet and not hot air bottles.
    Global Warmers models (a la Hansen) expected a kind of heated CO2 piggy bank to form in the tropical atmosphere, it never happened simply because it can not.
    If global warmers were to succeed in achieving their SUPPOSED goal of lowering CO2 level to nothing, life would disappear from the face of the earth.
    So, if no CO2 NO YOU!

  99. Richard S Courtney says:
    November 3, 2011 at 4:38 am

    “You disagree with Beck’s data because it has high variability, but that variability is its most important indication.

    At many localities the atmospheric CO2 concentration varies by hundreds of ppm between day and night.”

    This is true. That variation depends on where one measures the CO2 though as if that is in an urban area then the CO2 would be higher during the day when there are lots of cars pumping out CO2 and less during the night as it is mixed into the atmosphere.

    However if one examines the yearly average of atmospheric CO2 in isolated locations (there are dozens of these), the variability is low. These locations give a good measure of the global CO2 in the well-mixed atmosphere averaged on a yearly basis.

  100. Richard S Courtney says:
    November 3, 2011 at 4:38 am

    The ice core data show falsely low variability in atmospheric CO2 concentration. Real measurements such as those collated by Beck provide much more useful information.

    ————–

    If one actually examines the original papers from which Beck’s weird analysis descends, you find a bunch of wildly unrepresentative CO2 measurements made in cities. We know these give false measures of the globally averaged atmospheric CO2 levels since the scientists who made them point out, for example, that CO2 measures are 40 ppm higher in the afternoon than in the morning, and higher on windless days compared to windy days. These are clear indications of massive contamination of CO2 measures with industrial/human sources.

  101. Ferdinand Engelbeen says:
    November 2, 2011 at 2:20 pm

    Gail Combs says:
    November 2, 2011 at 12:58 pm

    Your argument is
    #1 No liquid phase occurs within the ice.
    #2 The process is entirely mechanical with no chemical or physical processes.

    In pure ice, there is no liquid water at the ice-air border below -32°C…..
    ____________________________
    Again you are making assumptions.

    The ice is not pure especially with volcanoes in the vicinity. I always has particulates and stuff like SO2. Also it only takes small amounts of liquid H2O to absorb the CO2.

    Actual Studies using a “wet method” (melted ices) and a “dry method” (crushed ice) done before the 1985 “Revisionism” showed there was less CO2 in the bubbles and more CO2 in the ice.

  102. It is truly about time that more scientists begin questioning the ‘CO2 trapped in glacial ice’ theory. It has been practically unassailable over the last couple of decades but I’m not sure if anyone really has taken a proper shot at it. I really have my doubts about it, the whole theory has far too many assumptions included in it. It just does not pass the sniff test in my view.

  103. Lucy Skywalker says:
    November 2, 2011 at 3:03 pm

    Gail Combs

    Thanks for sharing relevant (and IMO truly scientific) knowledge in spades….
    ______________________

    I am glad you uploaded the J&S paper. It does need to be looked at because it brings up good points. The paper points out the discrepancies in the data found before 1985 (using different methods) and the CAGW bless information in papers after 1985.

    The telling point for me is the quote from Solomon’s article:

    …in 1994 Dr. Jaworowski, together with a team from the Norwegian Institute for Energy Technics, proposed a research project on the reliability of trace-gas determinations in the polar ice. The prospective sponsors of the research refused to fund it, claiming the research would be “immoral” if it served to undermine the foundations of climate research …..

    http://www.nationalpost.com/news/story.html?id=25526754-e53a-4899-84af-5d9089a5dcb6&p=3

    Why would it be “immoral” if it was pure science? It could only be considered “immoral” if CAGW is the means that is being used by the United Nation’s IPCC to scare the “Great Unwashed” into accepting “Sustainability” aka the United Nation’s Agenda 21. (The great and noble worldwide implementation of socialism under the “guidance” of the international bankers. /sarc)

    Unfortunately we now must use the “Politics” and “Money” filters whenever we view the conclusions of “scientists” Cui Bono is the best method for lay people to filter out the BS.

  104. Ferdinand Engelbeen says:
    November 2, 2011 at 2:27 pm

    Gail Combs says:
    November 2, 2011 at 12:58 pm

    Forgot to add:

    The idea that the gases do not “Migrate” is idiotic. You have a crystal lattice with pores and water/brine AND tremendous pressure

    What is the difference in pressure between ice at 2000 m depth and 2000.1 m depth and how much migration does that induce? And how many still open pores are left at that static pressure? Even the bubbles did disappear…
    __________________________________

    AGAIN bad assumptions!

    Very simply gas is compressible and solids are not, although ice under pressure will have a tendency to melt at lower temps. Liquids are also not compressible either. Therefore the pressure will “Drive” the gas into the liquid.

    “A phenomenological description and a semiempirical two-zone model are proposed for the gas-liquid interfacial areas and the volumetric liquid-side mass-transfer coefficients in cocurrent downflow trickle-bed reactors operated at elevated pressure…..

    …It has been observed experimentally that, below a critical value of superficial gas velocity, gas holdup and mass-transfer parameters are unaffected by pressure. Beyond this critical velocity, increasing pressure enhances these parameters. This observation has been qualitatively interpreted assuming that, besides improving liquid spreading over the packing, high pressures also bring about high gas-liquid interfacial shears. As a result of the high momentum transfer, some gas is entrained and dispersed under the form of tiny bubbles in the liquid, thereby enhancing gas-liquid mass transfer and gas holdup….” http://teledosforum.dyndns.org:2206/%3ERESEARCH%20PUBLICATIONS/CHEMICAL%20ENGINEERING/Mass%20Transfer/Gas-Liquid%20Interfacial%20Mass%20Transfer%20in%20Trickle-Bed%20Reactors%20at%20Elevated%20Pressures.pdf

    The physical set up is the same, a thin film of liquid over a solid with a gas-liquid interface.

    Also at the air bubble/ice surface water molecules are only hydrogen bonded to their neighbours on one side. Consequently, their energy is not as low as in bulk ice. So, at equilibrium, they have a higher entropy allowing a thin water layer on the interface surface. ( http://www.animations.physics.unsw.edu.au/jw/freezing-point-depression-boiling-point-elevation.htm#pressure )

    Given this information plus the pressure plus impurities the presents of water in the liquid phase is highly probable.

    Chain of Cascading Lakes Discovered Under Antarctica
    Richard A. Lovett
    for National Geographic News
    February 16, 2007

    A series of connected lakes has been discovered deep beneath glaciers in Antarctica that is speeding streams of polar ice into the sea, scientists announced yesterday…. Some 145 have been charted, one as large as Lake Erie.

    http://news.nationalgeographic.com/news/2007/02/070216-antarctic-lakes.html

  105. Ferdinand;
    Last but not least, the physical impossibility:
    – an increase of 80 ppmv in only 7 years is not impossible, but highly implausible: that is the equivalent of burning down 1/3rd of all land vegetation on earth…>>>

    I don’t buy the reasoning. Your response discredits leaf stomata, and two sentences later you quote the lack of correlated leaf stomata to discredit Beck. Which is it? Are the leaf stomata accurate or not? Further, the sediment cores you quote, just as the ice cores, are lousy from a resolution perspective. Data with a resolution of 30 to 60 years or more just isn’t going to capture a rise and fall in CO2 over a 15 year period. Given all the uncertainties others have raised about the ice core data, is it such a stretch to consider that the spike Beck recorded could have been missed?

    As to the impossibility, again, I don’t buy your reasoning. Sure, burning 1/3 of the vegetation didn’t happen. Sure, a 10 degree temp increase in the oceans didn’t happen. But, one doesn’t need a SINGLE cause, there can easily be several causes that coincided. For example, while the “average” temperature of the earth in fact rose during that time period (another tough to explain coincidence) the SH rose by considerably more than the NH, and that is where the bulk of the world’s oceans are, so the amount of CO2 released due to ocean warming would be quite out of proportion to the “average” temp increase. Combine that with sudden retreat of ice sheets due to the temperature spike, and consider the amount of dead and rotting organic material that would suddenly be exposed in a short time period.

    I think if you stop trying to prove Beck wrong, and start to consider all the possible drivers that would have resulted in a CO2 spike that correlates to the temperature spike that correlates to the “divergence problem”, his results aren’t that much of a stretch at all.

  106. Tom Harley says:
    November 1, 2011 at 8:12 pm
    A very entertaining account, considering I have never seen snow, nor wish to…
    ______
    Never even seen snow, and don’t wish to? Quite sad on both accounts. Snow is one of the most wonderful things that water makes of itself…

  107. R. Gates says:
    November 3, 2011 at 12:12 pm

    “Never even seen snow, and don’t wish to? Quite sad on both accounts. Snow is one of the most wonderful things that water makes of itself…”

    —————-

    R. Gates,

    . . . . other than veddy veddy dry Plymouth Gin Martinis, of course.

    John

  108. Enneagram says:
    November 3, 2011 at 6:17 am
    It is advisable to remember a few facts:
    CO2 follows temperature, not the other way.
    ______
    It would be more advisable not to simplify this relationship. It is not always one way as sometimes temperature does indeed follow increases in CO2.

  109. Ferdinand Engelbeen says:
    “The coastal ice cores contain quite an amount of salts (ordinary salt, but also carbonates) blown in from the sea (as salt spray). ”

    Nice try, but not supported by the data. Have you looked @ Figure 3 yet?

    http://www.geocraft.com/WVFossils/Reference_Docs/CO2_diffusion_in_polar_ice_2008.pdf

    It clearly shows no spike in Ca (nor normally high enough levels) to consider sea spray relevant when the CO2 spikes to greater than 700 ppm. Besides that, look at the ECM, even the spikes are RO quality water. Nope, no sea salts there.

    Next explanation: “CO2 was removed from other layers above it.”
    Again, nice try, but nope, all the layers above it shown in figure 3 are actually above or @ normal. Hmmm, strange that scavaging and replacing CO2 meltwater magic.

    Want to try again? Where did the excess CO2 come from?

    Ok, let’s make it easier. Let’s say they rightfully expected 16k ppm(umol/mol) but then why only 700 ppm in the ice core? Does the ice only capture a fraction of the available CO2?

  110. R. Gates;
    It would be more advisable not to simplify this relationship. It is not always one way as sometimes temperature does indeed follow increases in CO2.>>>

    True. Clear evidence that the two are not directly correlated.

    Own goal! Gates scores another!

  111. It makes my day when scientists that should know better state that water and ice are not compressible. My ice 9 detector went off scale. Bulk modulus of water 2.2 E9 N/M*2, bulk modulus of ice 8.8 E9 N/M*2 (roughly).
    There are also some allotropic forms of ice.

  112. SteveE

    Your posts at November 3, 2011 at 7:30 am and November 3, 2011 at 7:59 am each claim to be answering my post at November 3, 2011 at 4:38 am.

    But your posts do not answer either of the points made in my post; viz.

    1. Observed variability of atmospheric CO2 at localities indicates that local CO2 sequestration can easily absorb all the natural and anthropogenic emission at each observed locality, and this falsifies the hypothesis that recent rise in atmospheric CO2 concentration (e.g. as measured at Mauna Loa since 1958) is a result of about half the anthropogenic emission accumulating.
    And
    2. The radiative greenhouse effect results from actual concentrations of GHGs in the atmosphere and not some hypothetical ‘background’ concentration, so if the CO2 concentration is high by day and low by night at localities then that has a direct effect on the magnitude of any putative radiative greenhouse effect.

    The fact that you make two posts which purport to address my post but ignore what I wrote strongly suggests that you think my points important so you want to discredit them but cannot.

    And your statement saying;
    “These are clear indications of massive contamination of CO2 measures with industrial/human sources.”
    is plain daft. The effect of “human sources” on the atmospheric concentration is what the measurements are intended to determine: the effect is NOT “contamination of” the “CO2 measures”.

    Richard

  113. Richard S Courtney says:
    November 3, 2011 at 4:38 am

    Richard, indeed we have had this discussion again and again over the years…

    In summary:
    At many localities the atmospheric CO2 concentration varies by hundreds of ppm between day and night. This indicates that local CO2 sequestration can easily absorb all the natural and anthropogenic emission in that locality.

    That is not the case. If you look at the modern local data of Giessen (one of the pillars of the 1942 “peak” of the historical data), the night increase is not compensated by the day absorption from photosynthesis. The reason: at night there is often less/no wind, which makes that much more CO2 from (soil/vegetation) respiration and human sources remains in the atmosphere. During the day, wind speed is higher and solar heat gives more vertical movements, which mixes the air layers up to more height. That makes that the CO2 levels at ground level in average are 40-50 ppmv higher than above 200 m and higher. Thus ground level CO2 over land is anyway positively biased. And highly variable. The Giessen samples were taken at 7 AM, 2 and 9 PM. That alone gives a 40 ppmv bias, compared to “background” CO2 (the latter represents over 95% of the atmosphere) and high variability as the 7 AM and 9 PM samples were taken at the moment that the highest changes in CO2 level are measured: 15 minutes later or earlier would give different results… Thus the historical data from Giessen are completely worthless to know what the CO2 levels in the bulk of the atmosphere at that time were.
    See: http://www.ferdinand-engelbeen.be/klimaat/klim_img/giessen_background.jpg
    and the differences of CO2 levels with height over land (Cabauw, Netherlands):

    So, when considering an anthropogenic contribution to atmospheric CO2 concentration one needs to explain why the local sequestrations do not dominate. and
    Indeed, the seasonal variations also indicate that local sequestration can easily cope with all the natural and anthropogenic emission.

    The local sources and sinks do dominate locally, that is in less than 5% of the atmosphere over land. The sum of all local movements ends up in the bulk of the atmosphere where it is visible as an increase over the years. The huge exchanges caused by the temperature changes over the seasons (mainly in the NH) are visible too. The result is that the seasonal changes near zero out over a year, with a net absorption of about 2 ppmv. Humans emit 4 ppmv per year. Thus nature can’t cope with the human emissions, or it would absorb all 4 ppmv…

    Furthermore, the radiative greenhouse effect results from actual concentrations of GHGs in the atmosphere and not some hypothetical ‘background’ concentration.

    You can use Modtran to see what the effect of elevated CO2 near ground is. Even a tripling to 1000 ppmv in the first 1000 m above ground level doesn’t (theoretically) increase the temperature with more than 0.1°C. Thus the real increase to 500-600 ppmv at night for the first few hundred meters is simply unmeasurable…

  114. aaron says:
    November 3, 2011 at 4:55 am

    Ferdinand, Liquid water in Antarctic glaciers.

    That report is about water under the basal ice. The last tens of meters of any glacier are at near zero temperature, due to earth warmth, where the glacier isolates the escape. Thus there you can find water. In the case of Antarctica probably even millions of years old. Despite of its isolation, that is full of microbial life… The bulk of the ice core at Vostok is at -40°C, there is practically no liquid water present, except around dust particles…

  115. John Whitman says:
    November 3, 2011 at 5:35 am

    Based on your about quote could you please give me references to exact passages in the talks or papers of Prof Jaworowski where you think he says there is “migration of CO2 from low levels to high levels.”?

    Of course, he doesn’t say that literally, but he implies that:

    From:

    http://www.warwickhughes.com/icecore/

    After decompression of the ice cores, the solid clathrates decompose into a gas form, exploding in the process as if they were microscopic grenades. In the bubble-free ice the explosions form a new gas cavities and new cracks[4]. Through these cracks, and cracks formed by sheeting, a part of gas escapes first into the drilling liquid which fills the borehole, and then at the surface to the atmospheric air. Particular gases, CO2, O2 and N2 trapped in the deep cold ice start to form clathrates, and leave the air bubbles, at different pressures and depth. At the ice temperature of –15oC dissociation pressure for N2 is about 100 bars, for O2 75 bars, and for CO2 5 bars. Formation of CO2 clathrates starts in the ice sheets at about 200 meter depth, and that of O2 and N2 at 600 to 1000 meters. This leads to depletion of CO2 in the gas trapped in the ice sheets.

    First, the opposite process, of clathrate decomposition, indeed happens at different pressures. Thus O2 and N2 clathrates decompose long before CO2 clathrates decompose. Thus if open cracks are formed, the internal pressure would lead to the escape of relative more N2 and O2 than CO2, leading to too high readings of CO2 levels. Not too low (clathrates violently decompose under vacuum at measuring time, that gives no problems for the measurements).

    Second, if CO2 clathrates decompose much later than O2/N2 clathrates, the cracks formed by O2/N2 new formed gas are already under near the same pressure as the outside world. As CO2 clathrates decompose there is very little increase in pressure, as CO2 is only 0.02-0.03 % of the previous atmosphere.

    Third. Even if all of the above doesn’t hold and all clathrates are decomposed back to the ancient air composition before cracks occur, the current outside atmosphere is at 390 ppmv (360-370 when most ice cores were measured), while one measures 180-300 ppmv in the bubbles. Thus, or the original CO2 level was much lower and is already enriched by the outside CO2 levels, or CO2 escapes preferentially faster than O2/N2 under the high internal pressure, which is highly unlikely as CO2 is far more retained by the water layer on the ice/air boundary than O2/N2, thus again leading to too high CO2 levels. And once that the internal and external pressures are the same, the higher outside CO2 level would migrate to the inside…

    Fourth, as the ice cores are relaxed during at least a year, there is plenty of time for migration in and out the ice core, if cracks play any role at all. In general, where real cracks are encountered, one always find too high CO2 levels, never too low, and in many cases one finds drilling fluid in the cracks.
    Moreover, repeated measurements many years later with better equipment show the same CO2 levels as before, not higher or lower…

  116. Gail Combs says:
    November 3, 2011 at 9:17 am

    Actual Studies using a “wet method” (melted ices) and a “dry method” (crushed ice) done before the 1985 “Revisionism” showed there was less CO2 in the bubbles and more CO2 in the ice.

    Actually the analytical world evolved since the early days of the first ice core drillings. The wet method retained too much CO2 in the liquid, therefore it is completely abandoned. The new sublimation technique evaporates everything and thus measures CO2 in bubbles and ice, but the crushing technique shows the same levels of CO2, although measuring only the CO2 in the bubbles (and what was sucked out of the pores in the ice).

  117. Caleb says:
    November 2, 2011 at 7:53 am
    OK, now for some fun.

    I have made it clear elsewhere that I’m not a scientist. I lacked the discipline necessary for science, and have an unruly imagination. I chose “The Arts,” and not “The Sciences.”

    I have great respect for true scientists, and would never be so rude as to tresspass on their territory, but they started it. By that I mean Climate Scientists left the strict confines of science, and tresspassed on my turf, which is the land of fiction, as opposed to fact. If they are going to so rude as to come horning into my landscape, well, I am going to defend my space.

    :) Not being a scientist I also decided that they having encroached on my turf… I’ve become quite fascinated by the fantasy world they’ve created, the atmosphere empty space where all molecules, except water, are without volume and zip around at tremendous speeds bouncing off each other and thoroughly mixing but not interacting because they have no attraction to each other and no weight so carbon dioxide defies gravity and accumulates for hundreds and even thousands of years forming a blanket, and so on. So I don’t look to these for information, but there are real scientists here and I expect someone will be able to explain what is puzzling me about ice core samples.

    So, carbon dioxide and water in the atmosphere have an irresistable affinity for each other in rain, fog, snow, dew, so stuff rusts, pure clean rain is carbonic acid. What we have is carbonic acid to add to the mix in these ice cores, isn’t it?

    What are they actually measuring then? If they’re crushing up these samples to get the carbon dioxide trapped in air bubbles these must somehow be not of the snow which was formed to ice in these layers because carbon dioxide as a gas didn’t exist in them, it’s all frozen carbonic acid, right? Are they also measuring any changes in the level of this carbonic acid in the ice as they have measurements for other concentrations of acids which came down in the snow? Or does this carbonic acid change back to water and carbon dioxide somehow?

  118. davidmhoffer says:
    November 3, 2011 at 12:09 pm

    Your response discredits leaf stomata, and two sentences later you quote the lack of correlated leaf stomata to discredit Beck.

    Leaf stomata data have their problems, because they measure land CO2, with a bias. That bias can be accounted for by comparing the stomata index data to the ice core data and direct measurements over the past century. But even that gives results +/- 10 ppmv. The stomata data should be used with caution further back in history, as nobody knows how the land bias changed over the centuries by climatic changes (e.g. wind direction during the LIA) and landscape changes (like marshes to forests, sea to polders, industrialisation,…). But a change of 80 ppmv around 1942 is as much change as over the full period 1900-2000. That would be visible as a sink of stomata index below the full scale of the graph I referenced. Thus if the stomata data have any value, they show that there was no 80 ppmv peak CO2 level in 1942, not even one of 10 ppmv.

    Further, the sediment cores you quote, just as the ice cores, are lousy from a resolution perspective. Data with a resolution of 30 to 60 years or more just isn’t going to capture a rise and fall in CO2 over a 15 year period.

    I agree that the resolution of sediments is even worse than from ice cores back in time, but that doesn’t change the average. If they show 180 ppmv during 90,000 years, then either there was much variability and levels were both (much) higher and (much) lower (the latter not that good for plant life on land), or there was little variability and some plant species even then would have problems.
    Further, the highest accumulation ice cores (2 out of 3 Law Dome cores) have a resolution of about a decade, sharp enough to detect a peak of 20 ppmv during one year or 2 ppmv during 20 years. Thus a peak of 80 ppmv spread over several years would be measurable in these cores and a lot of others, even with lower resolution.

    the amount of CO2 released due to [SH] ocean warming would be quite out of proportion to the “average” temp increase.

    That makes it even worse. If only the SH oceans were responsible, then the temperature increase needed would be 13°C as 70% of the oceans is in the SH. But that didn’t happen, the whole oceans increased at maximum 1°C since the LIA. That is good for a 16 ppmv increase, according to Henry’s Law or 8 ppmv in real life (as vegetation takes more away at higher temperatures)… Even if you combine all possible sources, it is near impossible to give such a peak in CO2.

    Moreover, we have had several periods of temperature increase, decrease, increase, flat temperature by now. CO2 levels show a not so good correlation with temperature over time, only a good correlation with increase speed… During decreasing temperatures (1945-1975), the CO2 levels further increase and as we have a flat temperature in the past decade, the CO2 levels increased as never before…

    I think if you stop trying to prove Beck wrong, and start to consider all the possible drivers that would have resulted in a CO2 spike that correlates to the temperature spike that correlates to the “divergence problem”, his results aren’t that much of a stretch at all.

    If skeptics would stop defending the indefendable work of the late Ernst Beck and Jaworowski, they would be more accepted on other items which are by far more debatable, like the real (lack of) influence of CO2 on climate…
    If two independent proxies plus direct measurements in high resolution ice cores don’t show any 1942 peak at all and a peak of 80 ppmv is implausable as increase and impossible as decrease in such a short period and all direct measurements since 1960 don’t show any huge variation at all for any natural changes (including sea surface temperature, vegetation changes, volcanic eruptions), then in my informed opinion there was no 1942 peak in CO2 levels…

  119. John West says:
    November 3, 2011 at 5:34 pm

    Nice try, but not supported by the data. Have you looked @ Figure 3 yet?

    http://www.geocraft.com/WVFossils/Reference_Docs/CO2_diffusion_in_polar_ice_2008.pdf

    It clearly shows no spike in Ca (nor normally high enough levels) to consider sea spray relevant when the CO2 spikes to greater than 700 ppm. Besides that, look at the ECM, even the spikes are RO quality water. Nope, no sea salts there.

    I had looked at that figure, seems quite logical that if you have percolation of water through the ice layer, that it will take some CO2 with it, especially if slightly alkaline. Anyway more than in pure water (the Ca values are low but not zero…). And you don’t know how many snow layers were passed before the water was refrozen. Refreezing itself also increases the CO2 level in the remaining, much fewer, bubbles, as the water contains far less O2/N2 than CO2, even if there was no or little enriching underway.

    But that all makes no difference in the results: based on the calculated migration, the theoretical broadening of the resolution is at maximum 10% at near 300 m depth (2.74 kyr old) and at full depth (60-70 kyr) the resolution is 100% wider. No problem at all, as that means 22 year averaging at 2.74 kyr gas age and 40 year averaging at 60 kyr gas age…

    For the much colder Vostok and Dome C ice cores, the broadening of the resolution is simply unmeasurable.

  120. Richard

    Your reply to my post November 4, 2011 at 12:46 am doesn’t answer either of the points I made;

    1. Yearly averages of atmospheric CO2 in isolated locations show low variability demonstrating that high variability measures shows contamination and hence are incorrect.
    2. Beck’s analysis which you seem to base most of your argument around is clearly wrong.

    The work done by Beck is widely discredited as the papers which his analysis is based on include wildly unrepresentative CO2 measurements made in cities. We know these give false measures of the globally averaged atmospheric CO2 levels since the scientists who made them point out that CO2 measures are 40 ppm higher in the afternoon than in the morning and higher on windless days compared to windy days. These show that the measurements are contaminated by industrial/human sources. If you think this is daft try taking a sample on Park Lane at 6pm and tell me that’s a representative sample of the global atmospheric CO2 content.

    The fact that you reply to both my posts but fail to address any of the issues that I raise suggests that you simply can’t defend the work done by Beck and his high variable CO2 measurements.

  121. Myrrh says:
    November 4, 2011 at 3:38 am

    So, carbon dioxide and water in the atmosphere have an irresistable affinity for each other in rain, fog, snow, dew, so stuff rusts, pure clean rain is carbonic acid. What we have is carbonic acid to add to the mix in these ice cores, isn’t it?

    Snow at the high elevations of Antarctica is formed at about -80°C. Not much water there on the surface of the flakes, not even at the average -40°C when it deposits on the surface. Thus there is little absorption, if at all on the snow. Accurate CO2 measurements are done with water vapour removal over a cold trap at -70°C. That removes most of the water below the detection limits of CO2 measurements, without affecting the CO2 levels…

  122. SteveE:

    I write so others are aware that I read your childish post at November 4, 2011 at 6:09 am

    Your two posts at November 3, 2011 at 7:30 am and November 3, 2011 at 7:59 am each claimed to be answering my post at November 3, 2011 at 4:38 am. but talked about other things: anybody can see that.

    And the fact that you made two replies to my post proves you knew your first reply was an inadequate response to what I wrote.

    Address what I wrote or – if you want – make your silly assertions (e.g. contribution of anthropogenic CO2 emissions to atmospheric CO2 concentration are “contamination” of atmospheric CO2 measurements). But do not pretend your silly assertions are a response to what I wrote.

    Richard

  123. Ferdinand:

    The rates of change to seasonal variations prove that local sequestration can easilly cope with the total of natural and anthropogenic CO2 emissions. We have debated this data so often that the sensible thing is for you to admit it instead of us going through all the information again.

    Richard

  124. Ferdinand Engelbeen says:

    I had looked at that figure, seems quite logical that if you have percolation of water through the ice layer, that it will take some CO2 with it, especially if slightly alkaline.

    “Seems logical”, well then let’s just stop using observation and experiments and just go with what seems logical.

    Anyway more than in pure water (the Ca values are low but not zero…). And you don’t know how many snow layers were passed before the water was refrozen.

    The Calcium is in the single digit parts per BILLION range, essentially nothing. For comparison sea salt has about 400 parts per million. Typical fresh water is in the ppm range not single digit ppb range. “The calcium concentration of water varies from 1 to 135 mg/L across the USA and Canada. Most spring waters were found to have a relatively low calcium concentration, with an average of 21.8 mg/L.” http://www.ncbi.nlm.nih.gov/pmc/articles/PMC2488164/
    Since mg/L is ppm, surely you can see that <10 ppb is actually very very LOW, such that we're back to the solubility of CO2 in fresh water ~ 4 ppm.

    Refreezing itself also increases the CO2 level in the remaining, much fewer, bubbles, as the water contains far less O2/N2 than CO2, even if there was no or little enriching underway.

    That sounds like something that could be tested experimentally. Do you have any data to back it up?

    But that all makes no difference in the results

    My questions are pertaining to the data and some assumptions made without basis not the results and conclusions (yet). They present data that clearly shows a large and rapid spike in CO2 captured in the ice core, claim incorrectly that this is due to high solubility of meltwater and incorrectly allude by reference that the meltwater is seawater and posit a huge “expected” CO2 value from an assumed 278 ppm atmosphere. You seem to be avoiding the questions, here they are again:

    Where did the “excess” CO2 come from?

    If there really should have been 16k ppm as was “expected”, then why did the ice only capture 700 ppm?

  125. Richard,

    You claim my post is childish and that I make silly assertions in another attempt to divert from the fact that you have based your whole argument around flawed analysis by Beck. My previous posts made no claim to have answered your two points, purely pointing out that parts of your post were wrong, yet you used this to try and change the direction of the discussion away from the points that were raised:

    1. Yearly averages of atmospheric CO2 in isolated locations show low variability demonstrating that high variability measures shows contamination and hence are incorrect.

    2. Beck’s analysis which you seem to base most of your argument around is clearly wrong.

    The fact that you have replied once again and fail to address either of the issues that I raise suggests that you simply can’t defend the work done by Beck and his high variable CO2 measurements. The reason you can’t defend it is because it is simply wrong.

  126. Ferdinand;
    That makes it even worse. If only the SH oceans were responsible, >>>

    Clearly, you missed the point. Let me try again:

    1. the “average” temperature of the earth increased considerably during that time period.
    2. the NH warmed, and the SH warmed MORE.
    3. So, the amount of CO2 released due to warming of the oceans would have been consideably higher than simply taking the average for the globe. The NH contributed, AND the SH contributed. While the NH contributed less than what the “average” would suggest, the SH contributed several times what the average would suggest.
    4. You’ve once again attempted to constrain the rise in CO2 reported by Beck by arguing against the existance of a single source. I never argued a single source. I argued that there are multiple sinks and sources and they are all subject to change, and if cycles from multiple sources coincided so as to reinfirce each other instead of cancelling each other, then the amount of CO2 measured by Beck becomes quite plausible.

  127. Richard S Courtney says:
    November 4, 2011 at 7:24 am

    The rates of change to seasonal variations prove that local sequestration can easilly cope with the total of natural and anthropogenic CO2 emissions.

    As said several times in the past: that doesn’t prove such thing. Seasonal variations are the result of temperature changes. That gives a huge, but rather fixed release and fixation of CO2 as well as in the oceans as in vegetation. If the temperature changes, the amount released or absorbed changes. If there is no temperature change, there is hardly any change in CO2 release/fixation.

    The seasonal variability of the combined oceans and vegetation is about 5 ppmv/°C. As the global temperature varies about 1°C over a year (mainly due to the NH land temperature), the global variation over the seasons is not more than 5 ppmv within a year.
    The year by year variability is about 4 ppmv/°C. There is a good correlation between the year by year variability of temperature and the variability in CO2 increase (in fact in CO2 sequestering).

    The emissions currently are at 4 ppmv/year continuously, thus in 2-3 years, the emissions by far exceed the natural variability.

    Thus the natural rate of change over the seasons copes with temperature changes but far less (about 50%) with extra added CO2.

  128. Ferdinand Engelbeen says:
    November 4, 2011 at 4:26 am
    davidmhoffer says:
    November 3, 2011 at 12:09 pm

    Your response discredits leaf stomata, and two sentences later you quote the lack of correlated leaf stomata to discredit Beck.

    Leaf stomata data have their problems, because they measure land CO2, with a bias. That bias can be accounted for by comparing the stomata index data to the ice core data and direct measurements over the past century. But even that gives results +/- 10 ppmv. The stomata data should be used with caution further back in history, as nobody knows how the land bias changed over the centuries by climatic changes (e.g. wind direction during the LIA) and landscape changes (like marshes to forests, sea to polders, industrialisation,…). But a change of 80 ppmv around 1942 is as much change as over the full period 1900-2000. That would be visible as a sink of stomata index below the full scale of the graph I referenced. Thus if the stomata data have any value, they show that there was no 80 ppmv peak CO2 level in 1942, not even one of 10 ppmv.

    SteveE says:
    November 4, 2011 at 6:09 am
    Richard

    Your reply to my post November 4, 2011 at 12:46 am doesn’t answer either of the points I made;

    1. Yearly averages of atmospheric CO2 in isolated locations show low variability demonstrating that high variability measures shows contamination and hence are incorrect.
    2. Beck’s analysis which you seem to base most of your argument around is clearly wrong.

    The work done by Beck is widely discredited as the papers which his analysis is based on include wildly unrepresentative CO2 measurements made in cities. We know these give false measures of the globally averaged atmospheric CO2 levels since the scientists who made them point out that CO2 measures are 40 ppm higher in the afternoon than in the morning and higher on windless days compared to windy days. These show that the measurements are contaminated by industrial/human sources. If you think this is daft try taking a sample on Park Lane at 6pm and tell me that’s a representative sample of the global atmospheric CO2 content.

    ============================================

    I think both these have views about Beck because of their preconceptions, their own biases. Beck makes perfect sense in my world where CO2 is local, the ‘background well-mixed’ an illusion, where levels fluctuated during the day depending on wind and photosynthesis, so for example, calm days will have higher levels because carbon dioxide being heavier than air will always sink displacing air unless work is being done to alter that, and so on.

  129. Caleb’s article is amusing and nicely written, but on this occasion I have to disagree with the doubts he casts as to the ability of air to diffuse from the surface down into packed snow.

    Experience from my teenage years of formative sociopathy included throwing stink-bombs (glass ampoules with some sulphurous solution) in public places – in those days stink-bombs could be bought from joke-shops, nowadays the health and safety frauleins would never allow it. It was remarkable to observe how fast the odour would diffuse through still air – much faster than we could run for example.

    So diffusion is fast – phenomena such as diffusion at the atomic level are in the realm of quantum mechanics where bizzare and unexpected things happen routinely where our empirical observations from the everyday world are of little value. Talk of grabacules etc. show that it is hardly worthwhile trying to visualise what happens at the atomic-quantum level. Air molecules have no difficulty at all diffusing into any and every available space at high speeds. For all we know, individual CO2 molecules could be quantumly smeared over a range of depths.

  130. davidmhoffer says:
    November 4, 2011 at 8:04 am

    It doesn’t matter much if only the SH oceans warmed, or the NH or both: the average temperature of all oceans increased with 0.2°C in the period 1935-1942 and decreased 0.1°C in the period 1942-1950. That is good for a worst case increase of CO2 in the atmosphere with 3.2 ppmv and a decrease with 1.6 ppmv in the “peak” period.

    Of course there was the 1940-1945 war, which destroyed a lot of houses, some vegetation, etc. Even if 5% of the world’s vegetation was destroyed, that would give not more than 15 ppmv extra, but even 5% is way too high for what was really destroyed (and regrowths fast)… And not visible in the 13C/12C record, as that would give an enormous drop in ratio.

    Volcanoes? Even the largest eruption of the last 60 years, the Pinatubo is inversally visible in the CO2 record, as the temperature drop did sink more CO2 in the oceans than the Pinatubo emitted. I am not aware of more volcanic activity in the period 1935-1942.

    Thus there is not the slightest indication that there was an enormous source at work during seven years and an enormous sink thereafter…

  131. Myrrh says:
    November 4, 2011 at 8:26 am

    I think both these have views about Beck because of their preconceptions, their own biases. Beck makes perfect sense in my world where CO2 is local, the ‘background well-mixed’ an illusion, where levels fluctuated during the day depending on wind and photosynthesis, so for example, calm days will have higher levels because carbon dioxide being heavier than air will always sink displacing air unless work is being done to alter that, and so on.

    I try to look at the facts, which are that there are places where there is very little variability in CO2 levels, and places where there is a lot of variability. In 95% of the atmosphere there is little variability in 5% there is huge variability. If you take the average over a year from places like Barrow near the North Pole via Mauna Loa to the South Pole ,from seaship surveys and airplane sampling, then you see the same averages (within 5 ppmv) and the same trend. That one can call background. That has nothing to do with bias but with facts…

    What Ernst Beck has done is compiling a lot of historical samples from a lot of places, where most were in the 5% high variability part of the atmosphere. Then he concluded that that represents the whole atmosphere of that time. And that is where my objections against his results are.

    I don’t think that you would agree with a temperature record where 90% of the data comes from the middle of large towns…

  132. John West says:
    November 4, 2011 at 7:32 am

    OK, I have read the first part of the report now too (I didn’t before, as I was only interested in the results).

    The researchers base their calculation on several points:
    – the concentration of CO2 in water at the surface of Siple Dome at equilibrium is measured/calculated.
    – a thin film of that CO2 rich water percolates through the firn until it encounters a layer cold enough to refreeze the water.
    – when that refreezes soluble gases are freezed out, that is CO2, Ar, Xe and Kr, O2 and N2.
    – these gases gets in a few bubbles left in the refrozen layer, part goes into adjacent bubbles and part escapes to the atmosphere by diffusion via still open pores.
    – how much CO2 should be retained in the surviving bubbles is calculated based on the Xe/Ar, Kr/Ar and 40Ar/36Ar ratio’s of the different ice parts and the ratio in ice/water volumes between the melted and normal ice parts.
    – then they compare the calculated retention of CO2 in the refrozen layer with the measured spread in the adjacent bubbles gradually away from the refrozen layers.
    – they attribute the CO2 spread away from the refrozen layer to migration over time. In my opinion, that is a rather dubious claim: if refreezing is relative slow but porosity is quite small, the diffusion speed is reduced, but still may spread the CO2 levels over adjacent layers before all bubbles are fully closed.

    About your questions:
    Where did the “excess” CO2 come from?

    According to the researchers, from the atmosphere by simple dissolving of atmospheric CO2 in liquid water until equilibrium.

    If there really should have been 16k ppm as was “expected”, then why did the ice only capture 700 ppm?

    The 16k ppmv was the ratio within water. While refreezing, CO2 is expelled from the ice into the present total bubble air volume, which gives an excess of 700 ppmv in air. Thus it is just a matter of water vs. air volume ratios…

    In this case I am not defending this work, as I think that there still are too many unresolved questions, but it is a an attempt for quantification of the migration speed of CO2 in ice cores over extreme long periods, which is near impossible to obtain from laboratory setups. My interest was in the results: a small increase to a doubling of the resolution. Not a real problem, and certainly not proof that ice cores are unreliable sources of information, as some seems to think that this report shows…

  133. Sorry, I need to leave this discussion now, will have a nice city trip to Barcelona in the next days… With restricted Internet access (and not much time, better things to do…).

    Ferdinand

  134. So what we are really saying here is that ice created in 1941 has air in it from the year 2001 and therefore any air sample taken from lower layers are all mixed/contaminated with the previous 60 years of atmospheric conditions? Which means no representation can be made as to the accuracy of ice core samples below that of a century scale and depending on the variability of atmospheric gas concentrations, the significant digit may be at 1% or more like 10%. That’s a pretty big error bar.

  135. Ferdinand Engelbeen says:
    November 4, 2011 at 6:58 am
    Myrrh says:
    November 4, 2011 at 3:38 am

    So, carbon dioxide and water in the atmosphere have an irresistable affinity for each other in rain, fog, snow, dew, so stuff rusts, pure clean rain is carbonic acid. What we have is carbonic acid to add to the mix in these ice cores, isn’t it?

    Snow at the high elevations of Antarctica is formed at about -80°C. Not much water there on the surface of the flakes, not even at the average -40°C when it deposits on the surface. Thus there is little absorption, if at all on the snow.

    Carbon dioxide is alreay in the flakes, unless you’re saying that the flakes aren’t made of water.

    Accurate CO2 measurements are done with water vapour removal over a cold trap at -70°C. That removes most of the water below the detection limits of CO2 measurements, without affecting the CO2 levels…

    So it isn’t measuring the carbon dioxide in these ‘air pockets’? But in the whole lot. But, they do have measurements of other acids and such from ice cores, where can I find the measurements for carbonic acid?

    Ferdinand Engelbeen says:
    November 4, 2011 at 10:15 am
    Myrrh says:
    November 4, 2011 at 8:26 am

    I think both these have views about Beck because of their preconceptions, their own biases. Beck makes perfect sense in my world where CO2 is local, the ‘background well-mixed’ an illusion, where levels fluctuated during the day depending on wind and photosynthesis, so for example, calm days will have higher levels because carbon dioxide being heavier than air will always sink displacing air unless work is being done to alter that, and so on.

    I try to look at the facts, which are that there are places where there is very little variability in CO2 levels, and places where there is a lot of variability. In 95% of the atmosphere there is little variability in 5% there is huge variability. If you take the average over a year from places like Barrow near the North Pole via Mauna Loa to the South Pole ,from seaship surveys and airplane sampling, then you see the same averages (within 5 ppmv) and the same trend. That one can call background. That has nothing to do with bias but with facts…

    Hi Ferdinand, I really don’t place any value on these ‘trends’, since they actually began when Keeling announced after less than 2years of data, that he had a positive trend that man made contributions of carbon dioxide were, etc. etc. Less than two years. What does that say to you? Have you read how they meaure CO2 levels there? They decide what is volcanic.. How the heck can they tell? And don’t give me, the other stations all show the same trend because first of all kept in the family, then taken over by ‘government’ which continues to produce this ‘trend’, Keeling began with an agenda to prove man-made contribution. That’s why he jumped at the chance of having an unlimited supply sitting on top of an active volcano, surrounded by active volcanoes, by continuous carbon dioxide earthquakes and other venting above ground and in the warm oceans around.. Yeah right, sold to us as “a pristine site for CO2 measurements, uncontaminated by local production”.. The only useful thing this graph shows is that carbon dioxide is unrelated to any temperature changes since it began..

    ..and, the only trend I see is that they are beginning to come to the Beck’s figures.

    What Ernst Beck has done is compiling a lot of historical samples from a lot of places, where most were in the 5% high variability part of the atmosphere. Then he concluded that that represents the whole atmosphere of that time. And that is where my objections against his results are.

    Carbon dioxide really doesn’t do tourism, Ferdinand.

    I don’t think that you would agree with a temperature record where 90% of the data comes from the middle of large towns…

    Apples and oranges. Carbon dioxide is heavier than air, wherever it is produced it is likely to stay in the general vicinity heading down displacing air, winds move it around, but, it’s not always windy. The atmosphere isn’t in a permanent tumble dryer. Plants exhale it too. This is what AIRS concluded, that it was clumpy, and they haven’t yet to my knowledge released any of the lower troposphere data, and as far as I know have never shown a proper telling of the mid troposphere. Unless one can get the raw data and do one’s own work on it, what they meant by lumpy isn’t readily seen. The bland picture they presented is mid-troposphere, could all be from planes that high…

    Enjoy Barcelona, lovely place, great food and Gaudi.

    =================================

    Caleb – more bubbles for you, http://chiefio.wordpress.com/2011/01/27/fizzy-sky-ir-spectrum-is/

    Appears that at -30°C carbonic acid goes into gas phase, not as widely believed, into water and carbon dioxide.

    http://www.sciencecentric.com/news/11011131-international-first-gas-phase-carbonic-acid-isolated.html

  136. Myrrh:

    At November 4, 2011 at 8:26 am you say;

    “I think both these have views about Beck because of their preconceptions, their own biases. Beck makes perfect sense in my world where CO2 is local, the ‘background well-mixed’ an illusion, where levels fluctuated during the day depending on wind and photosynthesis, so for example, calm days will have higher levels because carbon dioxide being heavier than air will always sink displacing air unless work is being done to alter that, and so on.”

    There are no ”preconceptions” on my part. Indeed, I completely agree with your view that I quote here.

    I twice attempted to provide a point-by-point refutation of the nonsense from SteveE but it has failed to appear. Perhaps the Mods can find it?

    Richard

    [REPLY: Can’t find the reply you are talking about. Please post again. -REP]

  137. Richard S Courtney says:
    November 5, 2011 at 7:13 am
    Myrrh:

    At November 4, 2011 at 8:26 am you say;

    “I think both these have views about Beck because of their preconceptions, their own biases. Beck makes perfect sense in my world where CO2 is local, the ‘background well-mixed’ an illusion, where levels fluctuated during the day depending on wind and photosynthesis, so for example, calm days will have higher levels because carbon dioxide being heavier than air will always sink displacing air unless work is being done to alter that, and so on.”

    There are no ”preconceptions” on my part. Indeed, I completely agree with your view that I quote here.

    I twice attempted to provide a point-by-point refutation of the nonsense from SteveE but it has failed to appear. Perhaps the Mods can find it?

    Richard – thank you for letting me know.

    I hope you can repost it, seems odd that it’s got lost – have just looked for it in part 1 in case.., or tackle writing it again.

    Re-reading some of the posts in part 1, I think this bias from Ferdinand is firmly in that he sees no reason to doubt the Keeling et al readings, and so naturally everything that is offered is fed back through that prism, for example, bacteria can’t be making that much of a difference, ‘because they don’t show up as making any difference in the ppm between the cores – http://wattsupwiththat.com/2011/10/31/little-bubbles-part-1/#comment-785325

    Indeed during glacial periods, there is less water vapour which gives less clouds and rain and, which brings more dust and bacteria even until far inland cores. But as the coastal cores always show much higher salt/dust/bacterial contamination and higher temperatures (-20°C vs. -40°C), that should reflect in the CO2 (and other) levels, but that is very limited: all ice cores are within 5 ppmv for the same periods in time…

    Whereas I look at that and think, I do hope they’ve kept somewhere a real record of it all for future use in the scientific endeavour.

  138. Richard S Courtney says:
    November 5, 2011 at 7:13 am

    I twice attempted to provide a point-by-point refutation of the nonsense from SteveE but it has failed to appear. Perhaps the Mods can find it?

    To save yourself the pain and drudgery of retyping and re-composing, install the Lazarus FireFox add-on. It automatically caches all typed entries in reply boxes, and you can specify how long to hold them. (default 14 hrs.; I have mine set for 54 weeks, just because.) Search the whole list, or right click in the relevant reply box and select “Recover text”, and you’re done.

  139. Myrrh says:
    November 4, 2011 at 4:24 pm

    Just back from sunny and warm Barcelona…

    So, carbon dioxide and water in the atmosphere have an irresistable affinity for each other in rain, fog, snow, dew, so stuff rusts, pure clean rain is carbonic acid. What we have is carbonic acid to add to the mix in these ice cores, isn’t it?
    and
    Carbon dioxide is alreay in the flakes, unless you’re saying that the flakes aren’t made of water.

    Carbon dioxide is quite soluble in liquid water but insoluble in ice or snow. Just try to freeze carbonated water: when it freezes, all CO2 is pushed out and if the bottle is not strong enough, it can explode… Thus all CO2 that you have in snow is in the air inbetween the ice crystals of the snow. When the snow compacts, as long as there are open pores with the atmosphere, there is exchange of air possible, including CO2. Slower with depth, depending of the ice density / pore diameter.

    So it isn’t measuring the carbon dioxide in these ‘air pockets’? But in the whole lot. But, they do have measurements of other acids and such from ice cores, where can I find the measurements for carbonic acid?

    Of course they are measuring CO2 from the air pockets: by crushing the ice at -40°C, the air from the pockets is set free. But even at -40°C, some water evaporates, from veins (if salts are present) or the surface (even solid ice evaporates under vacuum). At -70°C, most of the water vapor condensates under the detection level for CO2 measurements.

    Hi Ferdinand, I really don’t place any value on these ‘trends’, since they actually began when Keeling announced after less than 2years of data, that he had a positive trend that man made contributions of carbon dioxide were, etc. etc. Less than two years. What does that say to you?

    Well, that says that his measurements were accurate enough to see the increase over two years, long enough to show that the increase was larger than the noise. See here over a few years:

    Have you read how they meaure CO2 levels there? They decide what is volcanic.. How the heck can they tell? And don’t give me, the other stations all show the same trend because first of all kept in the family, then taken over by ‘government’ which continues to produce this ‘trend’

    Yes, I have read how they decide that CO2 from the volcanic vents is mixed in. That is quite simple: if the measurements show a high variability within an hour, then there is volcanic activity interfering. Opposite, if there are upwind conditions, then the levels go down, because of depleted by vegetation in the valleys, In both cases the variability increases to +/- 4 ppmv at maximum. But that doesn’t change the average or the trend with more than 0.1 ppmv! Since they started at Mauna Loa, the total increase is 80 ppmv. The variability around the trend thus is peanuts compared to the trend itself.

    Further, the measurements at the South Pole were first, before Mauna Loa: the same trend, but without the interference of any volcano or vegetation there…
    And how do you think that Scripps reacts on their loss of the supervision of the world’s CO2 measurements? By doing their own measurements, independent of NOAA. If there was anything wrong with the NOAA measurements, don’t you think that they would point that out?

    Carbon dioxide really doesn’t do tourism, Ferdinand.

    It does in the first 200 m of the atmosphere: there you can find any CO2 level you want to find. Over 1000 m and everywhere over the oceans, the levels are within +/- 10 ppmv everywhere in every season.

    Apples and oranges. Carbon dioxide is heavier than air, wherever it is produced it is likely to stay in the general vicinity heading down displacing air, winds move it around, but, it’s not always windy.

    CO2 stays low, if emitted in huge quantities at once. If released with small amounts, it is moved around by Brownian motion and only slowly settles out if completely stagnant, like in the case of snow layers: an enriching of 1% at the bottom of firn over a distance of 72 meters in 40 years… Thus CO2 is moved around as soon as it is released and readily mixed with all air layers over time.

    This is what AIRS concluded, that it was clumpy, and they haven’t yet to my knowledge released any of the lower troposphere data

    AIRS doesn’t measure the lower troposphere. They measure the middle troposphere. That shows differences of +/- 10 ppmv (+/- 2.5%) at maximum all over the earth, including seasonal changes, while 20% of all CO2 in the atmosphere is exchanged with other reservoirs. Thus, in my opinion, that is well (and fast) mixed.

    I think this bias from Ferdinand is firmly in that he sees no reason to doubt the Keeling et al readings, and so naturally everything that is offered is fed back through that prism, for example, bacteria can’t be making that much of a difference

    When I read that bacteria are present (but hardly survive) in the Vostok ice core, I want to know how that influences the CO2 levels. At the places where the highest concentration of dust and bacteria was found, that would give a worst case difference of less than 1 ppmv…

    I do make a lot of differentiation between genuine researchers like Keeling Sr., who devoted his entire life at keeping good records of the (still) best available techniques for measuring CO2 all over the world, and others who use these data for interpretation and political goals. Revelle and Keeling expected an increase of CO2, based on the limited capacity of the ocean surface waters to absorb all human emissions. But they saw that as beneficial, because of higher temperatures for agriculture. You seem to forget the timeline: Keeling started his first measurements in the 1950’s and the first continuous series at the South Pole in 1957, before the “global cooling” scare… And long before the “global warming” scare. Just read his fascinating autobiography:

    http://scrippsco2.ucsd.edu/publications/keeling_autobiography.pdf

    My impression is that a lot of skeptics don’t like the CO2 data, only because that is one of the cornerstones of the AGW scare. If that cornerstone is made of sand, the whole AGW scare is falling apart. Thus the CO2 data must be proven wrong with all means (or at least the origin of the increase must be natural), even if all observations show the opposite… As good as the ice core data must be wrong, because these show the same increase… Thus where is the bias?

    Regards,

    Ferdinand

  140. Myrrh says:
    November 4, 2011 at 4:24 pm

    Some comment at:
    Appears that at -30°C carbonic acid goes into gas phase, not as widely believed, into water and carbon dioxide.

    http://www.sciencecentric.com/news/11011131-international-first-gas-phase-carbonic-acid-isolated.html

    I have looked up what the amounts of carbonic acid in solution are. These are known: less than 1% of the amount of free CO2 and free CO2 is less than 1% of the total carbon in water, over 99% are bicarbonate and carbonate ions. Thus carbonic acid is less than 0.01% of total carbon in water when CO2 gets in solution. I don’t know how they made pure carbonic acid and how stable that is. I am pretty sure that it isn’t that stable, if you need to “freeze” it in liquid argon to find its structure. It seems mainly of academic interest, without much influence on CO2 measurements, but it may be of interest for the greenhouse effect of icy clouds, where temperatures are low enough and solid surfaces may act as a substrate…

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