Little Bubbles, part 1

I await the sequel with bated breath… has there been disallowed chemistry going on between water and dissolved gases when under high pressure? Have the been pH changes that change the solubility of CO- and H+ ions during a long period of non-STP conditions? Could there be some doubt about the validity of atmospheric CO2 concentrations from gas bubbles from 500 to 5,000 decades ago?
Whatever could it be? Whatever could it mean?

You are bound to get that reaction as you are hitting a little below the firn 😉

Baited Breath, I exhale!

I like your style of writing,very funny,but gets the message across.

I too have questioned those little bubbles, and the “science” based on them. Scientists are retrieving the air trapped in these bubbles and making assumptions that the air trapped in these bubbles is representative of the atmosphere at the time the air was trapped. For me, many questions pop into my mind about these assumptions.
How much of the CO2 becomes absorbed into the surrounding ice matrix, like CO2 in soda pop?
How much of the CO2 migrates through the ice, and is this migration at the same rate as the oxygen and nitrogen, or does CO2 concentration shift relative to O2 and N2?
How much CO2 is adsorbed by the ice crystal surfaces, does it release when the bubble is sampled, and does any of it get absorbed by liquid water during the sample process.
How much of the CO2 reacts with the water and forms carbonic acid?
Not that long ago I saw an article about viable micro-organisms being found in cores of ancient ice. How has the metabolism of these living micro-organisms affected CO2 concentrations?
Some molecules, like methane, can form hydrates with ice under cold and pressure; can CO2 form hydrates?
With cold and pressure, can small amounts of CO2 which migrate into the ice crystals congregate into pockets of dry ice?
Until every one of these questions was researched and definitely answered, I wouldn’t trust the absolute values of CO2 concentrations, though relative values might show trends with reasonable accuracy…

However just because Science focuses on the head does not mean Scientists have no hearts. “If you prick them, do they not bleed?”

I’d need to see the data.

But it’s the bubbles of nothing that make it really something …

Excellent writing from Mr. Shaw!

Calib; yes teenage girls are insane and change like the wind. Good news! they will become adults around 23 years of age. Until then, just try to bend a little with the breeze and in time they will calm.
As to the tiny bubbles, The science appears to me to be defective. Gasses are very mobil in water and ice, specially when pressures change. I suspect BS (bad science) pg

The fairy tale of objective science is why I left Anthropology and eventually ended up in Computer Science. I came up with all sorts of hieratical conclusions when examining the same data as the established priesthood – and I was ostricized for it. Nevermind many of my hieratical tenants eventually came to be main science – The priesthood protects their canon.
And so it is with Climate Science. And in 20 years sutdents will look back and wonder how stupid we all were – refusing to recognize that which was staring us in the face.
Emotions trumph logic. Ask the father of any teenager – girl or boy. And many of us never manage to grow up.
Good posting. It touched me… 🙂

I spent a lot of time looking into this and found all of the ‘science” is based on some very questionable assumptions.
1. Can you really obtain ice cores in the manner they did (with no effort to keep the cores under pressure) without losing the CO2 that was consolidated in hydrates? I say “No”.
This would be easily amenable to experimentation but I have never seen any evidence of such an experiment.
2. The way they shifted the axis in this work to cause the CO2 measured in the cores and modern atmospheric CO2 is very questionable. They based it on an assumption that the firn closes in about 70 yrs, merely an assumption.
3. They justify this on the basis of isotopic ratios (of O if I remember right) but the gases they used for isotopic analysis do not form hydrates (clathrates actually) as easily as CO2.
Until I see an experiment showing that CO2 in air consolidated in bubbles in compacted snow has the same ratio as CO2 in the air, their measurement is meaningless.

Caleb,
You write as well as Willis, but differently. I am very much looking forward to the next instalment.

@ davidmhoffer
Hello David,
I was never blessed with a girl (3 boys, 25,22 and 15)
One morning I woke up I was 40.
That day one of my teenage boys shuffled up to me with a wicked grin and said:
“Dad, how do you undo a bra?”
I went to bed that night at 50.
Boys not only teach you things…………..etc.
🙂

If the “bubble” scientists didn’t try to take into account the chemistry going on, they their results are all wrong. Changes in pressure, chemical reactions, UV light, will cause “chemistry” to happen in those bubbles. If the bubble-scientists just melted the ice and measured the gases, then their results are totally wrong. I always assumed these people had a semblance of competence and had chemists interpret their result to cater for the chemistry that went on over in the bubbles.

The only way you can be sure that bubbles are a proxy for atmospheric levels is to measure carbon dioxide at the time it is being “bubbled” and then come back 500 to 1000 years later to sample ice cores. Anything else is just speculation that some one-shot [snip . . cmon , you know the rules] has built a career upon (and perhaps I being a little unkind here since there are so many “scientists” forced into a one-shot, one-dimensional career by the politics of their situation – but then again it’s their choice to either call it as they see it or prostitute themselves to the job).
Bubbles in ice showing historical levels of carbon dioxide – c’mon, get real. Would you bet your retirement savings on stock in a company pitching that idea as a sure thing?
You would? Gee, I’ve got some carbon credit certificates for you – not too expensive. It’s my own company – we sequester carbon dioxide down at the local brew pub. Its a local. Its organic. It uses local suppliers. What more could you ask for?

>>
In any case, “Greenland ice cores” was history, and was history in a hurry, and was deleted history, which hardly counts as history because you can’t find it.
>>
Everything on Wikipedia (or any other content created with the software called Wiki, no it’s not the same thing) has an audit trail.
If you have lost the link to something important just look back through the edit history, find out who was doing the mass removals and compare old and new versions. You should find whatever you are missing.
I have not even looked at your link there yet but I can smell foetid odour AGW zealots already.
Indeed that this is clearly labelled as content removed solely on the basis of the author rather than any criticism of the content shows that WP is still in the hands of the zealots. Even after the exposure and temporary ban of William H Christ Connelly, WP has still not addressed the fundamental problem.

davidmhoffer says (October 31, 2011 at 8:54 pm); “One morning I was thirty six years old.
That afternoon, my 12 year old daughter gave me a great big hug, looked up at me with her great big eyes, and said, with a great big smile:
‘I need a bra!'”
HonEEEEE!

The hallowed BBC ran a 5 minute piece on bubbles in ice of antarctica the weekend. Now I am a long dead physicist and have been interested in climate/weather for some 50 yrs so I won’t claim to fully understand the chemistry but just to note what might seem obvious.
The over enthusiastic scientist, like a daughter and I have 2, cut a slice and said ” look at these bubbles, they are 80,000 yrs old. Then he cut another and said “these bubbles are 800,000 yrs old.
So what I hear you say. Well, there were far far fewer bubbles in the old slice than the more recent slice. Where had the bubbles gone if they are stable. IE If the gas cannot be transposed or change composition over time where have the bubbles gone??

GeologyJim and higley7 both mentioned the early CO2 studies of Ernst Beck. I don’t know which is marginally more precise: Beck’s wet chemistry or modern instrumental methods. To me, that question is not even interesting. But first, some background.
Precision means doing the ‘same’ measurement many times, and getting reasonably close agreement. It’s kinda like target-shooting with a revolver. If you manage to get a 1-inch group at 25 yards, then your precision is good. But that doesn’t mean that your accuracy is good. It’s very possible that your tight group is on the target’s outermost ring, rather than the bulls-eye that you were aiming at.
Anyway, precision is not the issue here. The issue is sampling error.
I’d expect there to be fairly large variations in measured values of CO2 taken in Europe in the late 19th and early 20th Centuries. And if my aging brain remembers correctly, that was in fact the case. If you had taken two CO2 measurements on two successive days, and if the wind had changed direction in the interim, I’d expect that you’d get significantly different values. Why? Forest fires, industrial smokestacks, cooking fires, etc.
Our present Mauna Loa-based system is much better. And it would continue to be much better even if we switched back to the slower wet chemistry methods that Beck used. Why? Much less man-made CO2 and forest-fire CO2 to gum up the works when we’re using that measurement as a proxy for global average CO2 concentration.
I don’t know what the global average CO2 concentration in the late 19th Century was, and I don’t know how I’d make that determination today. Perhaps geologists could help us to answer that question.

There is nothing more satisfying than seeing a core foundation of an accepted theory being demolished, as it means more theories can replace it, some may be better, some may not. But at least is allows progress to be made. These pauses while scientists all agree are what holds us all back. I am just hoping that the folk working on the Opera experiment in Cern do break the speed of light as it would open up that field of science to new ideas as well.

Dear Caleb,
I have looked at the basic assumptions of Jaworowski. His opinion is based on his knowledge, which ended in… 1992. Since then he obviously didn’t read any scientific literature, or he wilfully ignored it. Many of the objections he had were answered by the work of Etheridge, already in 1996, who worked on three ice cores at Law Dome. They used three different drilling techniques, wet and dry (no difference in results), measured CO2 levels in still open bubbles top down until closing depth (no difference between CO2 in ice and firn at closing depth) and they had an overlap of about 20 years (1960-1980) between direct measurements at the South Pole and in the ice core (no difference beyond the accuracy of the measurements). See:
http://www.agu.org/pubs/crossref/1996/95JD03410.shtml
unfortunately behind a paywall…
Jaworowski is completely wrong on at least two important points:
– 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.
– He accuses Neftel of using an “arbitrarely” shift in timing to allign the Siple Dome ice core CO2 with the Mauna Loa data. But he used the age of the ice layer, while the average gas age is (much) younger. He insists that the ice age and gas age are the same, while the difference was measured in the Law Dome ice/firn already in 1996.
These two points are already enough to ignore Jaworowski as ice core “specialist”.
See further:
http://www.ferdinand-engelbeen.be/klimaat/jaworowski.html
BTW, even if CO2 is hiding in clathrates or liquid veins of the ice, that doesn’t matter for the newest measurement technique: total sublimation and cryogenic freezing of all ice and subsequent selective measuring of the different components. This technique decomposes all clathrates and measures all CO2 and air components. The conventional technique by crushing the ice under vacuum at -20 degr.C over a cold trap (to remove water vapor) gives the same results.

My experience indicates that daughters and grey hair are synonymous…
Looking forward to Part Two… and keeping my fingers crossed you might provide some answers to the questions raised by Hans-Joachim Zillmer regarding the Greenland Icecore Project – GRIP where a bore core of 3,028 meters was extracted before bedrock was encountered.
1) If this ice core represents 250,000 years then each year’s snowfall has been compressed into 1.2 centimetres of ice [on average].
Is this true?
Is this valid?
How old really is the ice cap?
2) The uppermost sections display 14,500 distinct layers which are assumed to represent a year.
Is this true?
Is this valid)
Can more than one layer accumulate in a year?
How many years do these layers really represent?
3) How does anyone determine the age of the ice beneath the layered section?
4) Are the last 100,000 years of the ice core really compressed down to only 1 millimetre annually?
5) Do we really know the fluid dynamics of deep ice?
6) Do we really know the chemistry and dynamics of gases and particles buried in deep ice?

I always preferred clear ice in my cocktails, http://www.instructables.com/id/make-crystal-clear-ice!/
.But the Antarctic Ice Cores would make an interesting conversation ice. I would have to start with just the right temperature water at the right air pressure to get the carbonic acid ratio just perfect for bubble distribution and count.
Served with carbonated ice cream, http://www.boston.com/news/science/articles/2005/08/28/mit_crew_churns_out_ice_cream_with_sizzle/ it could be an interesting party.

Aahh, Ice bubbles…… Aren’t they some sort of tiny crystal balls?

Not sure about the science behind the tiny bubbles, but the following science may reassure some of you that there are chemical reasons for your sons’ and daughters’ behaviors. (Internal chemistry, not the other.)
http://www.parade.com/news/2010/11/28-inside-the-teenage-brain.html

Who will Ridley me of these meddled bubbles?
============

From the Wikipedia thoughts:
“Person B : Climate may be complex bit that doesn’t mean we can’t make predictions….”
Sorry but to me, that is a stupid statement. Of course one can make predictions about the future climate…they will be wrong every time, but you can make predictions 😉
Jeff

ggm says:
October 31, 2011 at 11:57 pm
I was told just the other day on this board that the chemistry of CO2 has nothing to do with ‘warming’ as it’s a ‘physical’ process. Of course, there was no explanation provided. It must have been covered by the ‘consensus’.

Nick Stokes says:
October 31, 2011 at 8:51 pm
It has long been suspected that low levels of radiation are good for you.

“The only thing a scientist is suppose to be passionate about is being dispassionate, however in their quieter moments most will confess there have been times they’ve failed to be totally objective, and have slapped themselves on the forehead because they were blind to some obvious truth staring them in the face.”
There is a group called “The Union of Concerned Scientists” that is always stoking doomsday fears, usually about nuclear war. The name always struck me as odd as I would be more likely to listen to a “Union of Unconcerned Scientists”.

Knowing absolutely nothing about this I’ll throw in my 20 cents worth and then you can all use me as the “Dodo Reference Point” 🙂
I thought that as time went past, volcanic ash fell on top of the ice, and then as more snow fell and more ice was made, layers were formed ; knowing when the eruptions occurred thus gave a time reference for how much CO2, sulfur, methane, etc .. came to ground and was trapped between the ice layers.
Knowing that (roughly) 41% of CO2 falls to ground, 44% in the frozen areas and 14% on the ocean one can then work out the total CO2 for any age.
The timing of the eruptions being known through archeological research on land, I think they are called sedimental layers.
The “Dodo Reference Point” thus asks … Am I right or …. wrong?
Very interesting blog, nice read.

That’s it, just question everything.
First you ask, is it really warming? Then you ask how much did it really warm? Then you follow up with questions like has it ever warmed like this before? Is it truly unprecedented? Is the data any good? Are the models accurate? Are the stations well sited? Are greenhouse gases really driving climate change? Is the peer-review process corrupted? Did some researches conspire to keep dissenting work from being published? Is the urban heat island effect underestimated? Is the scientific method being followed? Are the AGW predictions accurate?
And now you want to know if the ice core data is reliable! The next questions surely are, are gases truly sealed in those ice cores, or does some leak out? Is the historical atmospheric CO2 record derived from the ice cores accurate, or does it underestimate the amount in CO2 because the ice does not permanently trap CO2 as assumed? Was the pre-industrial revolution level of CO2 really as low as the ice core data appears to indicate?
Sheesh, what is it with you guys? You just question everything! Can’t you let these climate scientists have a little attention? Must you spoil everything?
Sometimes I think you’re just resentful of people who get more press coverage than you do.

Nick Stokes says:
October 31, 2011 at 8:51 pm
petermue says: October 31, 2011 at 7:52 pm
“This man is a real and truthful climate scientist.”
He isn’t a climate scientist. His regular job was/is
“Zbigniew Jaworowski is chairman of the Scientific Council of the Central Laboratory for Radiological Protection in Warsaw and former chair of the United Nations Scientific Committee on the Effects of Atomic Radiation (1981–82)”
But the post could be right – bubbles may do strange things. Here is Zbig explaining why radiation is good for you.

And Einstein was a nobody working as a patent clerk when you wrote an amazing series of paper in 1905. No doubt many of Einstein’s detractors liked to bring that up rather than provide meaningful criticism of the science.

Allan M says:
November 1, 2011 at 6:38 am
Volker Doormann says:
November 1, 2011 at 12:00 am
It is meaningless to speak on that what NOT is, because it has no existence. Science is a method to understand what IS.
Well, that all depends on what the definition of ‘is’ is.
Sorry, No. It is a fallacy: That what IS, depends on nothing. If that what IS would depend on something, the order of nature would not be recognizable as one</ order.
Something – of that what IS – cannot be true and in the same time be untrue, and because of this it is impossible to define it, without to define a contradiction. Science does not believe in contradictions.
V.

According to one paper I’ve read (Ho, Don, Journal of Hawaiian Music, 1966), researching those tiny bubbles will make you feel happy, make you feel fine

I left out a “not” in the last sentence. Researchers “cannot” say …

Volker Doormann says:
November 1, 2011 at 7:43 am
Allan M says:
November 1, 2011 at 6:38 am
I see the irony evaded you.

Shevva says:
November 1, 2011 at 5:00 am…………………………
Please remember I’m trying to get a climate grant so this maybe just what Stanford or some such Uni is looking for for new revenue streams, if you could make the cheque out to Mr Udgunda of Nigeria please.
——————————
Oops, you forgot to include your bank account number so I can deposit your check.

If it’s important, don’t go to Wikipedia, or Snopes. They are only good for settling alcohol lubricated bar bets.
I have empathy for any man who has had teenage daughters. I remember those days, and the parental pain that went with adolescent female hormones. On the other hand, I am the one she goes to when there’s a problem, like, money.
Now, she has her own daughter, and boy-oh-boy, is she in for it!

Leaving Jaworowski aside, there is a rich and growing literature dedicated to understanding microbial growth and survival in cold environments, specifically glacial ice. Perhaps the main proponent of this investigation, though there are many others, is Buford Price (NAS member). He brought this investigation to the forefront with his article,
Temperature dependence of metabolic rates for microbial growth, maintenance, and survival,
PNAS 2004 101 (13) 4631-4636; doi:10.1073/pnas.0400522101
http://www.pnas.org/content/101/13/4631.full
Over the past decade, I have become less surprised at every publication of where microbes can survive, if not grow. An early study found microbes in the snow at the South Pole at a concentration of ~10^3 cells/cm^3 with ~15% being from the Deinococcus-Thermus group. These are the hardy extremophiles, resistant to just about everything. Deinococcus radiodurans is the Guinness “world’s toughest bacterium”, able to survive 5,000 Gy of ionizing radiation (humans die at 5 Gy).
Finding them is one thing, but are they alive? Are they metabolizing? The answer is yes to both. Carpenter et al. (Applied and Environmental Microbiology, October 2000, p. 4514-4517, Vol. 66) reported incorportation of precursors into both protein and DNA at ~ -15 C for cells trapped in ice at the South Pole. The extent to which they are metabolizing is a different, thornier issue.
Another question is where are they living? From the above discussion, we have read about veins of “unfrozen” water and the possible diffusion of gasses, minerals and organic compounds through them. Several studies have shown that bacteria survive and metabolize in these environments, though very, very slowly. All the while, they are exchanging CO2, N2O, CH4, etc. with their environment. Price and colleagues have also suggested that another environment is conducive for supporting metabolism and viability: within the ice crystals themselves. From the abstract of the paper, Diffusion-controlled metabolism for long-term survival of single isolated microorganisms trapped within ice crystals, they state,
“…microbe[s] frozen in ice can metabolize by redox reactions with dissolved small molecules such as CO2, O2, N2, CO, and CH4 diffusing through the ice lattice.”
http://www.pnas.org/content/104/42/16592.full.pdf+html
No doubt, the diffusion and partitioning of small molecules like CO2 in glacial ice is not a trivial matter. Ice is not the equivalent of zircon, and chemistry and metabolism do occur at temperatures found in polar glaciers. The influence of a metabolizing microbial community on measurement of past CO2 concentrations is, in my book, an open question. I should also note that photosynthetic bacteria are also found in glaciers and that their chlorophyll content increases with depth (sorry can’t find the reference or talk right now). Moreover, chlorophyll containing bacteria are not the only ones that can incorporate CO2: bacteria with both proteorhodopsin and phosphoenolpyruvate carboxylase (think C4 plants) can at least incorporate some CO2 but cannot survive on CO2 alone. The involvement of these bacteria in the carbon cycle is only now being investigated.
Why haven’t we heard about these biological stories before? My guess is that interest in growth of bacteria in these extreme environments has been limited to the environmental microbiology, astrobiology, and origin of life communities. Implications of measuring gas and metabolite diffusion through ice and their in situ biosynthesis on proxy measurements of green house gasses is never brought up in these papers: why incur the wrath of climatologists whose ice cores you depend upon to do your work?
Microbes have shaped and continue to shape the composition of our biosphere. It would not be surprising to me if they also shape the glacial environment as well.

jason says: November 1, 2011 at 10:31 am
“I to have wondered about the little bubbles. The entire co2 house of cards rests on that one cornerstone. Evidence that historic co2 levels may have been higher than the cores record would destroy the entire unprecedented and dangerous nonsense.”
Jason – you said it all!
When it is shown that the bubble stuff is rubbish the entire house of cards collapses.

Volker said: “Climate is order and is solved.”
(http://www.volker-doormann.org/climate_code_s.htm)
Volker, have you read the work of Ivanka Charvátová?
http://www.mitosyfraudes.org/Charvatova_SIM.pdf
Although she’s looking from another perspective it seems you both look at the same temperatur driving mechanism, principally.

Volker Doormann says:
November 1, 2011 at 12:00 am
“It is meaningless to speak on that what NOT is, because it has no existence. Science is a method to understand what IS. That what IS is order. No one can show what not IS.”
Allan M says:
November 1, 2011 at 6:38 am
“Well, that all depends on what the definition of ‘is’ is.”
Volker Doormann says:
November 1, 2011 at 7:43 am
“Something – of that what IS – cannot be true and in the same time be untrue, and because of this it is impossible to define it, without to define a contradiction. Science does not believe in contradictions.”
Allan M says:
November 1, 2011 at 6:38 am
“I see the irony evaded you.”
T. Kobashi et al. have analyzed bubbles: “Persistent multi-decadal Greenland temperature fluctuation through the last millennium in an ice core from Greenland”.
I have analysed the heliocentric movement of (six) solar objects for the last millennium:
http://volker-doormann.org/images/greenland_ghi_5x.gif” .
I wrote above: “Climate is order and is solved
The point is, science is able to verify the outward manifestations of nature, because they are visible for all, but science is not able to verify the consciousness of an other person.
Logic and metaphysics are the basis of science and philosophy. No one can show the reference from that he is able to recognize truth. This reference is neither an object of democracy nor of bloggers, nor of a busy mind.
V.

petermue says:
October 31, 2011 at 7:52 pm
This paper from Zbigniew Jaworowski is better and more expressive.
It describes the scientific deficiencies of ice cores, physical defects, and why anthropogenic CO2 can’t be the cause for global warming based on his calculation.
http://www.warwickhughes.com/icecore/IceCoreSprg97.pdf
This man is a real and truthful climate scientist.
_____________
AMEN
For the laymen there are pdfs including much of Jaworowski’s work at Segalstad’s site: http://www.co2web.info/
It is well worth reading (References to various papers are included)

petermue says:
October 31, 2011 at 10:35 pm
Nick Stokes says:
October 31, 2011 at 8:51 pm
He isn’t a climate scientist. His regular job was/is
“Zbigniew Jaworowski is chairman of the Scientific Council of the Central Laboratory for Radiological Protection in Warsaw and former chair of the United Nations Scientific Committee on the Effects of Atomic Radiation (1981–82)”
In case of ice cores, and that’s the actual subject, he’s in the field of climate science.
I know Zbig …
For me, there were no 180 ppmv at the last glacial ….
__________
For me the 180 ppmv was the real killer. If it actually got that low we would all be dead.
“200 pm CO2 trees starve” http://biblioteca.universia.net/ficha.do?id=912067
but the link no longer works…
But there is this reference (they missed the practical greenhouse references in the purge I guess)
…. photosynthesis can be halted when CO2 concentration approaches 200 ppm… (Morgan 2003) Carbon dioxide is heavier than air and does not easily mix into the greenhouse atmosphere by diffusion… Source
You are not going to have healthy growing plants if you go below 200ppmv
This may be why Zbigniew Jaworowski got interested. He smelled something rotten.
In the paper by Tom Quirk “ Sources and Sinks of Carbon Dioxide” The isotopic balance in the atmosphere is far more complex and there are many more variables than most think. Consider 94% of all anthropogenic CO2 is released into the northern hemisphere. Next the CO2 is not as well mixed as the IPCC state. From the nuclear tests in the 60’s the mixing north to south is very slow, like several years ( another rhetorical question) so why is the average northern hemisphere CO2 not higher than the south?
I worked in industry sampling solid and liquid batches and the phrase “Well Mixed” instantly sets off alarm bells. If a kettle with no additional inputs and sophsysticated mixers can successfully and frequently screw up mixing I very much doubt the atmosphere is “well mixed” with just the wind and thermals.

Richard S Courtney says:
November 1, 2011 at 3:04 am
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.
Richard, CO2 dissolves in water. Right. But that is as good for CO2 from outside the core as from inside. Thus with an outside CO2 level for some periods more than twice the inside CO2 level, CO2 would migrate from outside to inside via water vains, ultimately pushing the inside CO2 level equal to the outside if that mechanism was at work at all.
But even the influence of any hiding of CO2 in water veins is proven wrong: the newer method sublimates all ice at very low temperature under vacuum, where ALL CO2 present is measured quantitatively, no matter if that was originally in the bubbles or in liquid veins. But that doesn’t indicate higher CO2 levels than the standard method where only CO2 from the bubbles is measured by crushing the ice under vacuum.
Further, as said before, the average air composition outside the bubbles at closing depth was measured in situ by Etheridge. There was a difference of 30 years between the average air age (compared to direct measurements at the South Pole) and the ice age (measured by counting the layers) at that depth (and no difference with the air already enclosed, as measured by the standard ice crushing method). According to Jaworowski (1992 and personal correspondence in 2009) there is no difference in age of ice and gas…
Further, I don’t “belief” that the ice core CO2 measurements are right, I am pretty sure that they are right, because a lot of people from a lot of organisation of a lot of countries do measure them under the best analytical circumstances, looking for possible artefacts and avoid them or correct them… And all ice cores, taken under extremely different circumstances of temperature, precipitation and contamination show similar CO2 levels (+/- 5 ppmv) for overlapping periods.
And as you know, I don’t “belief” that the current increase of CO2 is man-made. I am pretty sure that that is the case, based on the fact that the increase fits all available evidence and that the two main possible sources: oceans and vegetation are proven sinks for CO2. And because all possible alternatives I have heard of conflict with one or more observations. For those interested:
http://www.ferdinand-engelbeen.be/klimaat/co2_measurements.html#The_mass_balance

Gail Combs says:
November 1, 2011 at 1:37 pm
For me the 180 ppmv was the real killer. If it actually got that low we would all be dead.
Fortunately for land plants (sea plants don’t have that problem, plenty of CO2 in the oceans), the levels of CO2 near the surface are much (30-50 ppmv, up to several 100’s in the morning hours) higher than in the rest (95%) of the atmosphere, so that they could survive even at 180 ppmv “background” CO2 levels…
why is the average northern hemisphere CO2 not higher than the south
Tom Quirk was completely wrong on this point: he used a method to determine the NH/SH CO2 lag over the months, which doesn’t make a differentiation between 2, 14 or 26 month lags or alternatively 10, 22 or… month leads. In reality, there is a near 1.5 year lag of the SH CO2 level after the NH CO2 increase and there is a 0.5 year lag with altitude:
http://www.ferdinand-engelbeen.be/klimaat/klim_img/co2_trends_1995_2004.jpg

petermue says:
November 1, 2011 at 3:14 am
Sorry, but you forgot one thing:
The only point where ice cores show the real value is at the top layer.
As soon as that layer was covered by new snow/ice and is exposed to pressure, it loses CO2 by outwashing, degassing and diffusion.
If that was true, then there wouldn’t be any change from 180-280 ppmv as seen in several ice cores of sufficient length (at least 20,000 years), as the diffusion would be at work during 800,000 years for the oldest ice of Dome C. And as Etheridge showed: the ice core record at Law Dome and the atmospherice levels overlap for the period 1960-1980:
http://www.ferdinand-engelbeen.be/klimaat/klim_img/law_dome_sp_co2.jpg
Futher, there are extreme differences in temperature (from -20 to -40°C), extreme differences in accumulation (from a few mm/year for Vostok and Dome C to 1.5 m ice equivalent at Law Dome), thus extreme differences in pressure and possible migration speed. Despite that, all ice cores show nearly the same CO2 levels (and the same HS shape) for the same time frame:
http://www.ferdinand-engelbeen.be/klimaat/klim_img/antarctic_cores_001kyr_large.jpg
Last but not least, the theoretical migration was calculated from the Siple ice core, based on CO2 migration near remelted ice layers. That shows that the migration broadens the resolution (that is the averaging period, but that doesn’t change the average!) at middle depth from 20 to 22 years and at full depth (70,000 years old) from 20 to 40 years…

Gail Combs says:
November 1, 2011 at 1:37 pm
For me the 180 ppmv was the real killer. If it actually got that low we would all be dead.
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Ferdinand Engelbeen says:
November 1, 2011 at 2:57 pm
Fortunately for land plants (sea plants don’t have that problem, plenty of CO2 in the oceans), the levels of CO2 near the surface are much (30-50 ppmv, up to several 100′s in the morning hours) higher than in the rest (95%) of the atmosphere, so that they could survive even at 180 ppmv “background” CO2 levels…
____________________
The logic of that answer does not work.
If the levels of CO2 near the surface are “higher than in the rest (95%) of the atmosphere” then where the heck are the glaciers??? In the stratosphere?
And do not tell me the CO2 is lower at the poles than elsewhere because there are volcanoes at both poles.
Here is Becks information from Barrow Alaska.
Date – – – – Co2 ppm * * latitude * * longitude * * *author * * location
1947.7500 – – 407.9 * * *71.00* * * -156.80 * * *Scholander * *Barrow
1947.8334 – – 420.6 * * *71.00* * * -156.80 * * *Scholander * *Barrow
1947.9166 – – 412.1 * * *71.00* * * -156.80 * * *Scholander * *Barrow
1948.0000 – – 385.7 * * *71.00* * * -156.80 * * *Scholander * *Barrow
1948.0834 – – 424.4 * * *71.00* * * -156.80 * * *Scholander * *Barrow
1948.1666 – – 452.3 * * *71.00* * * -156.80 * * *Scholander * *Barrow
1948.2500 – – 448.3 * * *71.00* * * -156.80 * * *Scholander * *Barrow
1948.3334 – – 429.3 * * *71.00* * * -156.80 * * *Scholander * *Barrow
1948.4166 – – 394.3 * * *71.00* * * -156.80 * * *Scholander * *Barrow
1948.5000 – – 386.7 * * *71.00* * * -156.80 * * *Scholander * *Barrow
1948.5834 – – 398.3 * * *71.00* * * -156.80 * * *Scholander * *Barrow
1948.6667 – – 414.5 * * *71.00* * * -156.80 * * *Scholander * *Barrow
1948.9166 – – 500.0 * * * * *71.00* * * -156.80 * * *Scholander * *Barrow
Finally Jaworowski was made an example of . He was ridiculed and fired. The rest of the sheep scientists fell back in line. I have certainly seen several real life examples of that method of “Team Building” and Anthony has reported other cases here at WUWT.
There are trillions of dollars riding on “CO2 is increasing and the Temperature is increasing and MAN CAUSED IT. ” Any hole in the “Message” is going to get plugged.
“The few who understand the system, will either be so interested from it’s profits or so dependant on it’s favors, that there will be no opposition ….” — Rothschild, 1863
For those who are not interested in money “we are lying to save the environment” or “we are lying to bring about social equality” works just fine.

petermue says:
November 1, 2011 at 1:29 pm
@Volker Doormann
You can find Earth’s temperature gradient in lots of other data, like Sun’s MUV, magnetic flux and
i.e. all the great historic Minima.
Solanki et al.
http://www.umweltluege.de/pdf/solphys-2004.pdf
(Fig. 4)
How can the Sun copy Earth’s temperature gradient? 😉
There are a storks on houses of people in Germany where are babies have come. That seems interesting. But the very point of argumentation is that there are also fresh new babies in winter in Germany, when there are absolute no storks next to the houses, they have moved to Africa.
Such a point is the fact that the variation of the terrestrial temperature anomaly in the last half century correlates with the variation of the measured temperature anomaly of the planet Neptune:
http://www.volker-doormann.org/images/hadcrut3_vs_neptune.gif
The same effect is known to the planets Uranus and Pluto.
Question: ‘How can the increasing CO2 content in the atmosphere of the Earth increase the temperature of Neptune?’
Answer: ‘Wrong question. The question suggests that the rising temperature on Neptune is related to the rising CO2 content on Earth. But that is an weak argument. A more strong argument is that a common variable heat source drives a heat current to both Earth and Neptune and all the other outer bodies.
But it seems this is still a taboo.
V.

Ferdinand Engelbeen,
saw a cool animation yesterday:
Not quite what I had been led to believe!!

kuhnkat says:
November 1, 2011 at 5:19 pm
saw a cool animation yesterday:
Not quite what I had been led to believe!
What you see are the changes from vegetation and oceans due to seasonal temperature changes.
Well mixed doesn’t mean that all CO2 levels at every moment are equal. It means that any change at one place is mixed within all parts of the world in a reasonable time period. An increase at sealevel in the NH of 2 ppmv/year (that is 0.5% of the total CO2 level) needs a few weeks to distribute over the same latitude and altitude, a few months for other latitudes and altitudes in the same hemisphere and a few years to level off over the hemispheres. But as there is a continuous increase mainly in one hemisphere and a cyclic change in opposite ways between the hemispheres, there still are a lot of differences visible over monthly to yearly averages, be it less than +/- 5% of the values for monthly averages and less than +/- 1% for yearly averages.

Ferdinand Engelbeen:
The difference is that the poles are free from sources and sinks…
The poles are precisely where the solubility of CO2 in water is highest:
http://docs.engineeringtoolbox.com/documents/1148/solubility-co2-water.png
In other words, “Seawater that is colder can hold more CO2”:
http://www.aph.gov.au/library/pubs/climatechange/theclimate/oceans.htm
So atmospheric CO2 should sink faster at the poles, keeping polar levels below the global average. Correct?

Ferdinand,
Thank you for your reply. Indeed, ammonia oxidation by this one group of microbes would change CO2 concentrations by 1 ppm. But (there is always a but), you have to consider that this is one metabolic product that was measured. That is, the excess N2O is only one of several potential metabolic products that a variety of different bacteria could produce. If you could point me to papers on other metabolic products, such as acetate and formate, found in glacial ice, I certainly would appreciate it. 140,000 years of bacterial metabolism, albeit horrendously slow, could certainly affect local CO2 concentrations well above the 1 ppm, mentioned above.
In support of your implied conclusion that microbial activity does not significantly affect gas concentrations Rhode, Price, Bay & Bramall state in a follow up,
From the point of view of its value as a climate proxy, it is
fortunate that the concentration of atmospheric CO2 in the ice is so
high relative to the microbial concentration that CO2 excesses or
deficiencies caused by in situ microbial metabolism are unlikely to
be detectable except in basal ice that was formed on a highly
concentrated microbial habitat, such as was present in wetland
before glaciation.
http://www.pnas.org/content/105/25/8667.full.pdf+html?with-ds=yes
While I have no evidence to the contrary and thus take ice core CO2 measurements as a good first approximation (even better with the total sublimation data), I would certainly like to see analyses of what was left over in the sublimation studies. Acetate, I suspect, would not be volatile at the temperatures and pressures for such experiments and as for formate, I wouldn’t hazard a guess. Moreover, cells that do happen to grow, even if their doubling time is measured in kyr, could in principle draw down CO2 concentrations into nonvolatile compounds.
An alternative hypothesis with regard to CO2 concentration is that during relatively dry glacial periods, there is an increase in microbial cell concentration in the glaciers. Through photosynthetic and other processes, the CO2 in the ice is fixed in a higher proportion compared with relatively wet interglacial conditions. There might be a lower bound concentration for these processes, ~200 ppm?, and thus the low CO2 concentrations, and CH4 for that matter, found during maximal glaciation periods could in part reflect a slow but persistent metabolism by a diverse microbial community. Who knows? One way to test this is to determine the total carbon content per unit volume and compare it with the CO2 concentration. If microbial metabolism has no effect, then total C should be directly proportional to CO2. Conversely, if there is a is an effect, it would show up as a lower ratio of CO2/total C.
I am not sure of your DNA repair reference. I should note that bacteria devote ~25 % of their energy production (ATP and redox) to what is referred to a maintenance energy, the amount required for survival. DNA repair is not in and of itself a large energy consumer, but for a cell to perform DNA repair, it has to maintain overall energy, synthesize the repair enzymes, and have a proper concentration of dNTP. In fact, there are several such systems that function in every cell. For a cell to survive, it must also maintain its membrane integrity and fluidity, a proton gradient across the membrane, have the proper transport and redox proteins within their membranes, the proper set of enzymes to harvest energy, carbon, nitrogen, etc., be able to detect and degrade misfolded proteins, synthesize replacements for these degraded proteins,and the list goes on. Given all that a cell requires just to stay alive, I am astounded that they can survive at all, and in some cases, thrive in what we refer to as extreme environments.
One last tidbit, I have heard, but haven’t followed up, that photosynthetic bacteria have been found in communities associated with deep sea thermal vents. What light are they harvesting? Light from neutrino/dark matter collisions? Who knows? I only bring this point up since the history of microbiology has been consistently marked by “that can’t happen”/”it would contribute nothing” statements, that are usually overturned when people actually look carefully.
Thank you for your patience and your persistent scientific grounding. It has certainly helped to keep my feet on the ground when it comes to thinking about the carbon cycle etc. Last fun fact to know and tell: there are ~10^31 bacteriophage on earth and can devour up to 50 % of a cell population per day in ocean environments.

petermue says:
November 1, 2011 at 6:23 pm
Some more comments on:
There are good reasons to avoid stations like Mauna Loa, or even near ocean stations, because they could give wrong measurements per se. See
http://carbon-budget.geologist-1011.net/ (paragraph 1.2)
I had read that some time ago.
It would be very interesting to see that volcanic vents are the cause of the increase, as that would imply some teleconnection between human emissions and volcanoes, as the increase in the atmosphere is average halve of the emissions in the past 160 years. Moreover, the yearly average trends at Barrow, Mauna Loa, South Pole and 70 other stations are similar, only with a lag for altitude and a NH/SH lag:
http://www.ferdinand-engelbeen.be/klimaat/klim_img/co2_trends.jpg
where it is clear that Barrow is leading (better visible in detail), far from any known volcano…
About 139,096 active submarine volcanoes, that exhaust estimated ~25 GtC/y, that is far more than assumed man-made CO2!
Land based volcanoes and vents emit less than 1% of what humans emit (based on several measurements around volcanoes), sea floor vents may emit (much) more, but that is not of interest: they emit under great seawater pressure, thus most is absorbed in the deep oceans. The deep oceans have some limited exchange with the atmosphere via the THC (and other) sinks and upwellings, but more important, both near all volcanic vents and the (deep) ocean waters have a high 13C/12C ratio, compared to the atmosphere. If the (deep) oceans and/or volcanic vents were responsible for the increase in the atmosphere, then the 13C/12C ratio of CO2 in the atmosphere would increase, but we see a steady decrease in ratio, as well as in the atmosphere as in the ocean surface:
http://www.ferdinand-engelbeen.be/klimaat/klim_img/sponges.gif
Thimoty Casey is wrong about the 13C/12C ratio of volcanoes: all volcanoes I have read of were between -7 and +7 per mil d13C, where deep mantle volcanoes are at the low side and subduction volcanoes at the high side. But in every case, the volcanic vents were all above the current -8 per mil of the atmosphere. Fossil fuels are average at -24 per mil…

Caleb says:
November 1, 2011 at 8:59 pm
However I think we can safely say the science is not settled, even concerning a cornerstone like the icecore records.
I never believed in holy cows, to the contrary, that includes cows in India, whales and polar bears for Westerns, etc… Only when there is good evidence for the reliability of the observations, I will accept them, based on facts, not because the “mainstream” says so. In the case of CO2 measurements in the atmosphere and in ice cores and the available evidence about the cause of the increase of CO2 in the atmosphere, I agree with the “mainstream” and not with many skeptics.
My impression is that many skeptics use any possible (even implausible) straw for every subject that directly or indirectly supports the AGW “consensus”. That makes that the case where the real battle needs to be fought, the real impact of the CO2 increase on climate, is weakened by at least dubious claims on items where the science is really strong…
BTW, I have two daughters too. I survived their teenage time… The oldest follows my wife as teacher, the other inherited my technical skills and travelling mood and is flying around the world as helicopter pilot…