Guest essay by Robert Balic
A summary of a problem with estimates of the average concentration of carbon dioxide in the atmosphere and questioning of how it is possible that the rate of increase correlates well with global temperature anomalies.
I saw an interesting plot in the comments of of WUWT a while ago. It was based on the work of Murray Salby who pointed out the strong correlation between the concentration of carbon dioxide in the atmosphere (NOAA ESRL CO2 at Mauna Loa) and the integral of mean global temperature anomalies. How well the CO2 levels correlate with various temperature anomalies can be seen in this plot of the derivative of CO2 levels with respect to time (rate of CO2 level increase) alongside some estimates of global temperature anomalies – HadSSTv3 SH (southern hemisphere sea-surface temperatures) and RSS (lower troposphere temperatures from satellite observations).
http://woodfortrees.org/graph/esrl-co2/mean:12/derivative/scale:3/plot/hadsst3sh/from:1958/offset:0.3/plot/rss/offset:0.2/from:1990
The first time that I saw this, I thought that what was meant by “derivative” was an estimate from differences between consecutive months but in ppm per year (as time is in years) so I was twelve times as confident that something was amiss as I should have been. Even after realizing that the results were in ppm per month, I thought that the results were still implausible. That changes in sea surface temperature would have an effect on CO2 levels is plausible but to correlate so well and then to be measured so precisely in order to be able to see the correlation did not seem possible.
In the above plot, the CO2 levels in ppm per month were scaled by 3 to compare with temperature anomalies. If I were to use ppm per year, then I would divide by 4 to do the same comparison iehey are not the same dimensions so the scaling is irrelevant. The data clearly needs to be scaled and also offset to fit each other well so by good correlation I am referring to the way they differ from a line of best fit after scaling to have the same slope.
I have put this out there in comments on blogs and received few replies. One that I need to mention is the claim that the derivative values are some sort of concoction and are so small that they are negligible, about 0.03% of CO2 levels. I don’t know why I need to point this out but an average of 0.125 ppm per month is the rate of change of CO2 estimated using the same method since even Newton was a boy and is equal to 90 ppm per 60 years. Its not negligible but there is the question of whether the uncertainty in measurements are too large to see fine trends over a period of a few years (and you should never multiply the quotient of two values of different dimensions by 100 and call it a percent).
Eyeballing the graph, it appears that the data needs to be very precise in order to see a correlation and a little bit of math makes things clearer. Rather than using the above derivative of smoothed data (12 month moving mean), I took the CO2 levels from woodfortrees.org and the difference between values 13 months apart. Essentially the same with the results being in ppm per year.
There is a good fit to the global temperature anomalies, especially RSS lower troposphere after 1990 (and to HadSSTv3SH before 1990) when the rate of change of CO2 levels is scaled by 0.26 and offset by -0.30. The mean absolute differences between the two is 0.13 and the standard deviation (SD) is 0.17 but varies from 0.08 to 0.2 for blocks of 1 year .
Using the lower value, this is consistent with an uncertainty in GTA of 0.1 K and in monthly CO2 levels as low as 0.34 ppm as calculated using
0.26^2 x 2ΔCO2^2 + ΔT^2 = (2 x 0.08)^2 where ΔCO2^2 and ΔT is the random error of CO2 levels and GTA which would be 2SD of repeat measurements.
This assumes that when differences are at a minimum that it is solely due to random error in the two measurements but its worth remembering that HadSSTv3NH differs much more than this from the rate of CO2 change so there are obviously other errors. Its also a stretch to assume perfect correlation of the real values, especially since its claimed that CO2 levels have increased due to human emissions and the latter have been at a steady rate for the last three years. There is also the question of why such a good correlation with SH sea-surface temperatures and not NH, and why should the correlation be so perfect when things like changes in ocean currents should have a large effect on how much is sequestered into the depths of the oceans.
So unlike I first thought, the precision didn’t need to be ridiculously good to see the correlation but this is still to good to be true.
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Bindidon
– the effect of even tiny trace gas concentrations due to their ability to increasingly close the atmospheric window (8 to 12 µ).
Henry says
That cannot be the CO2 that is doing it, as there is no absorption of CO2 in the 8-12 um. That radiation 8-12 is not restricted by the CO2 at all…… CO2 absorbs strongly in the 14-15 um area which really carries very little energy [coming from earth] so the heat entrapment effect is very small.
I think Ferdinand is beginning to understand my argument. He knows that he still needs to come up with a balance sheet showing me how much sunshine is deflected by the CO2. There are absorptions of CO2 in the spectrum of the sun in the UV, 1-2 and 4-5 um which must be compared to the 14-15 of earth’s spectrum. My argument is that the net effect of more CO2 in the atmosphere is probably that of cooling rather than warming, or it is simply close to zero. You are on the right track to say that trace gasses do influence the global T. Trenberth calculated that ozone is responsible for the major portion of all that is being deflected by the atmosphere back to space….. So, we must look at the [trace] gases in the atmosphere that deflect the incoming energy. Unfortunately, Trenberth simply forgot about the peroxides and nitrous oxides that are also being manufactured by the most energetic particles coming from the sun. With the current lower magnetic field strengths on the sun, more of the most energetic particles are able to escape, forming more ozone, peroxides and nitrogenous oxides. Earth is defending us -i.e. you and me – by forming more of those essential trace gasses. That this is happening I can show you here:
As the ozone, peroxides and nitrous oxides increase, TOA, it will allow less UV in the oceans. Hence, global cooling is already here. That is what my data say. I am skeptical of UAH as well (Mr. Spencer) mainly because I know there is no probe material that can withstand what is now coming out from the sun. How many times can you make corrections for degeneration {what version are we in now] until the probe is done?
True enough. In science, you can only trust yourself and your own results. That is why I want to challenge you to measure for yourself. Anyway, if you look at my results (Tmin), how much cooling are we talking about?
It is not much…..???
[btw
there never was a ozone hole either. What with more OH radicals above the oceans it appears likely to me that peroxides are formed preferentially to ozone. But nobody measured the peroxides in the hole……..now take a peek at the spectrum of H2O2 and compare it to the spectrum of ozone]
henryp April 13, 2017 at 2:07 am
Bindidon
– the effect of even tiny trace gas concentrations due to their ability to increasingly close the atmospheric window (8 to 12 µ).
Henry says
That cannot be the CO2 that is doing it, as there is no absorption of CO2 in the 8-12 um. That radiation 8-12 is not restricted by the CO2 at all…… CO2 absorbs strongly in the 14-15 um area which really carries very little energy [coming from earth] so the heat entrapment effect is very small.
CO2 is what forms the ‘frame’ of the ‘window’, without CO2 the ‘window’ would extend to an even higher wavelength. CO2 absorbs near the energy peak of the earth’s IR emission spectrum which is why it’s such an important GHG. The reference to ‘trace’ gases. in the post Blindidon refers to is that even gases at very low concentrations can have an effect if they absorb in the ‘window region’, ozone for example at 10µm, and the freons.
I think Ferdinand is beginning to understand my argument. He knows that he still needs to come up with a balance sheet showing me how much sunshine is deflected by the CO2.
Sunshine is not deflected by CO2, it is absorbed but only in the very low energy tail of the irradiance spectrum.
henryp on April 13, 2017 at 2:07 am
That cannot be the CO2 that is doing it, as there is no absorption of CO2 in the 8-12 um.
1. CO2 8-12 µ: over 20,000 absorption lines
http://fs5.directupload.net/images/170413/6eeuglms.png
2. H2O 8-12 µ: less than 3,000 absorption lines
http://fs5.directupload.net/images/170413/luyodbwu.png
But… we should not forget that Spectralcalc has output here two logarithmic plots differing by 2 units in the scale. If we now let SC ouput a chart with 2 superposed linear plots we clearly see that CO2 is invisible.
3. CO2 + H2O 8-12 µ (linear)
http://fs5.directupload.net/images/170414/nx4acyjp.png
What is more important here? The number of lines or their intensity? Only persons with appropriate scientific education might give an answer. Storytelling is useless!
Phil.
Clearly, you have not been following my discussion with Ferdinand which I shall repeat for you:
If you want to prove to me that more CO2 causes warming, you have to present a balance sheet of how much radiation is deflected/back radiated away from earth where the sun emits 0-5 um in the areas where CO2 absorbs and how much is retained 24hr/ day by the absorption of CO2 in the 14-15 um range where earth emits , in both cases by the odd 100 ppm extra. This cannot be done with a closed box experiment and neither can it be done “with a satellite’.
I have suggested a type of experiment that you could try in a later comment. Unfortunately, nobody has carried out such a type of open box experiment.
Particularly, graphs 6 (bottom) and 7 of the report below prove my point that the CO2 is also cooling the atmosphere, i.e. absorptions of the CO2 in the 1-2 um that we picked up via the moon i.e. we can qualitatively measure the energy (radiation) reflected from earth by the CO2 via the moon
http://astro.berkeley.edu/~kalas/disksite/library/turnbull06a.pdf
Phil. it is clear that for anyone to see that your statement is incorrect. We can pick it up the suns’ radiation that was deflected by the CO2 EVEN VIA THE MOON COMING BACK TO EARTH. That is quite something.
For those interested here I can just mention again that I think they currently use one of the absorptions of CO2 in the UV range to identify the presence of CO2 on other planets. We are exactly seeing the things that are not possible according to phil. as [knowing from my past with him] he keeps on saying: ‘Sunshine is not deflected by CO2’
there are none so blind as those who do not want to see. I think I won’t talk to him again unless he admits that there is some sunshine that is deflected by the CO2.
henryp,
You are a little too fast, I have more than work enough to react in the discussion about the origin of the extra CO2 in the atmosphere: human or not. Looking at the solar/earth radiation energy absorption/deflection by CO2 is not high on my agenda now, thus I still have no solid opinion on that item…
Ferdinand
the question whether the added CO2 to the atmosphere is natural [due to more heat] or human induced [due to burning of fuels] is irrelevant if it is proven that the net effect of more CO2 is zero or close to zero with respect to [unnatural] global warming.
I have told you my findings.
https://wattsupwiththat.com/2017/04/07/questions-on-the-rate-of-global-carbon-dioxide-increase/#comment-2471429
If the cause of global warming were the CO2 it would be that the rate of warming must be more or less the same all over the world. That is not what is happening. Only a fool carries on and on about what really are toilet issues [on a global scale]
henryp April 13, 2017 at 6:39 am
Particularly, graphs 6 (bottom) and 7 of the report below prove my point that the CO2 is also cooling the atmosphere, i.e. absorptions of the CO2 in the 1-2 um that we picked up via the moon i.e. we can qualitatively measure the energy (radiation) reflected from earth by the CO2 via the moon
http://astro.berkeley.edu/~kalas/disksite/library/turnbull06a.pdf
You misunderstand the experiment you refer to.
Sunlight will pass through the atmosphere be, reflected from the Earth and reflected back to us from the moon. What is reported is sunlight which has made a triple pass through the atmosphere and will show absorption in the various bands due to H2O, CO2 etc.
Phil. it is clear that for anyone to see that your statement is incorrect. We can pick it up the suns’ radiation that was deflected by the CO2 EVEN VIA THE MOON COMING BACK TO EARTH. That is quite something.
You are mistaken, there is no deflection by CO2, there is absorption followed by thermalization (lower atmosphere) and reradiation (predominantly upper atmosphere).
For those interested here I can just mention again that I think they currently use one of the absorptions of CO2 in the UV range to identify the presence of CO2 on other planets. We are exactly seeing the things that are not possible according to phil. as [knowing from my past with him] he keeps on saying: ‘Sunshine is not deflected by CO2’
Less light will be reflected from the earth in the spectral absorption regions of CO2 compared with the adjacent regions of the spectrum. Perhaps you should define what you mean by ‘deflection of sunshine by CO2’, since it’s not a term used in science?
Phil. Bindidon
The GH effect (trapping some heat on earth) and the radiation that bounces off from earth before it even reaches the bottom, is the same process. The way from the bottom to the top (8-15um, emission from earth) is the same as the one top to bottom (0-5um , emission from the sun), Deflected sunlight (i.e. earth’s albedo) is the same process as the trapped radiation by GH effect on earth 8-15um. I am not going into semantics with phil. about that again. You can look at the spectrum of the substance/gas to determine/predict its effect on the GH or on earth’s albedo. There are very few gases that are completely permeable at all wavelengths. This is basic understanding. You may call the affected light deflection, reflection, mirror effect, re-radiation, back radiation, whatever.
As long as you understand that it means light is being sent back mostly in the direction where it came from. [just like when you put bright lights on in misty conditions: the light comes back to you].
Guys,
I am going to leave at that. I think I tried my best to explain things to you all so you may understand it a little better.
I am wishing you a good pass over and a Happy Easter. If you have doubts about the existence of God, perhaps give some thought to what I wrote here:
http://breadonthewater.co.za/2017/02/20/if-god-exists-why-cannot-we-see-him/
Best wishes
Henry
OK, this has all gotten rather esoteric, a bit buried in the weeds, so lets just revisit the basic fact. CO2 is plant food.
Simply genial, 2hotel9!
Why weren’t we all able to think of that?
You are the guide we missed all the time.
Montre-nous la voie, ô vénéré prophète!
I’m just not a believer in the “CO2 is evil” dogma. I see people who appear to be quite intelligent wasting their time on research that effects nothing. In the final measure humans are not causing the planetary climate to change, it just does, and neither can we stop the climate from changing. I mean damn, talk about hubris, humans just are not all that important in the grand scheme of things. Perhaps they should take a step back and get some perspective. Take all their energy and intelligence and do something positive for humanity, cuz this ain’t it. May some grand technological/scientific breakthrough that brings prosperity and peace for humanity? Maybe. So far all it has done is divide people even further and waste vast amounts of money/capital/resources which could have gone to something productive.
And with that my document print run is finished and I gots to trot. Two ondemand hotwater heaters to replace and finish out a stair case before we can wrap it up for the Easter weekend. Y’all all have a Hoppy Easter. And keep exhaling that CO2! The planet needs more.
I am going to repost something from above into a new thread here, because I think it gets to the nub of Ferdinand’s misunderstanding.
—————————————————
The point is that, the atmosphere has nothing to do with it, and is beside the point. It is just riding upon the ocean’s back.
So, you get a temperature increase. Downwelling at the surface level carries less CO2 down, so the surface level increases. This drives the downwelling faster.
In your world, it stops there, and it takes only a short while to reach an equlibrium condition.
But, the THC extends all the way down to the depths of the oceans and back up again. So, the upper level is induced by the added CO2 to transport more CO2 down. But, it is then resisted by the next layer of ocean, which is tuned to the previous volume of downwelling. That resistance now has to be overcome.
Then, the downwelling encounters the next level, and its resistance also has to be overcome.
You have to keep doing this all the way down, and it takes a very long time before a new equilibrium can be achieved. As long as you have an imbalance between what is upwelling, and what is downwelling, you will get an increase in the level at the surface. And, you will not equilibrate the downwelling to the upwelling until every level of resistance has been overcome.
Bart,
You simply don’t understand anything of basic physical processes. That is the problem.
Bart:
the atmosphere has nothing to do with it, and is beside the point.
Bart, please! The atmosphere has everything to do with it as there is no internal CO2 transport within the waterflow from upwelling to sinks. None at all. Diffusion of CO2 in the water mass is 12 orders of magnitude smaller than the speed of the water mass itself.
ALL changes in CO2 content of the waters is via the atmosphere (and a small part by the biopump into the deep oceans), not backward or forward in the water phase.
So, you get a temperature increase. Downwelling at the surface level carries less CO2 down, so the surface level increases.
Bart, can you give in detail how CO2 in the surface water level does increase, while less is transported from the upwelling areas to the sink areas and less is going down with the sinking waters? How does that CO2 move from sinking waters in opposite direction of the water flow to increase the local CO2 levels nearby/at the sinks? Or how does CO2 retains itself from sinking down with the water flow? Or do you think that elevated temperatures create more CO2 out of the blue?
This drives the downwelling faster. But, it is then resisted by the next layer of ocean, which is tuned to the previous volume of downwelling. That resistance now has to be overcome.
I am completely confused now. Are you talking about the total volume of water or the CO2 content which have nothing to do with each other? Even if there was a tenfold increase in CO2, you would hardly see any difference in water volume.
CO2 has no influence whatever on the downflow water volume or speed. Temperature and wind does have an influence, but that is mostly temporary (seasonal, El Niño), the rest is good for a Holywood disaster film…
This is a reply to Ferdinand’s points here as well as above. Trying now with a different link to the graphic of ocean currents.
“You simply don’t understand anything of basic physical processes that is the problem.”
Quite the contrary, I understand quite well that you have a simplified view that simply does not apply in this world.
“Thus there is no CO2 accumulation in the ocean surface with increasing temperatures, there is an overall decrease of CO2 in the full ocean surface.”
Again, you are living in a static universe. New parcels of CO2 are being released from upwelling waters every second to replenish what is lost, and keep pushing it on upward.
Again, this is a very simple, and legitimate, mass balance argument. If you have a set amount upwelling, and you restrict downwelling, then you must have an accumulation. That accumulation will continue until an equilibrium in the flow is reestablished. As the THC takes many centuries for circulation, that is the order of time that is required to reestablish equilibrium.
“Pressure IS at least an energy carrier or not much would work in this world.”
But, it is not unique to the atmosphere. Increasing atmospheric pressure does not drive more CO2 to downwell. Increasing overall content of the waters does. Atmospheric pressure is a symptom of the increasing content of the waters, not the cause. More on this point in the next response directly below:
“The atmosphere has everything to do with it as there is no internal CO2 transport within the waterflow from upwelling to sinks.”
Absolute nonsense. There are powerful ocean currents and gyres the world over. Take a look:
http://www.aoml.noaa.gov/phod/soto/gsc/currents.jpg
“Bart, can you give in detail how CO2 in the surface water level increases, while less is transported down with the sinking waters.”
CO2 laden waters are continually upwelling. If less is transported down with downwelling, then where do you think the excess goes?
“Are you talking about the total volume of water or the CO2 content which have nothing to do with each other?”
Always talking about the transport of CO2. Why on Earth would you think differently?
“You simply don’t understand anything of basic physical processes that is the problem.”
Quite the contrary, I understand quite well that you have a simplified view that simply does not apply in this world.
“Thus there is no CO2 accumulation in the ocean surface with increasing temperatures, there is an overall decrease of CO2 in the full ocean surface.”
Again, you are living in a static universe. New parcels of CO2 are being released from upwelling waters every second to replenish what is lost, and keep pushing it on upward.
Again, this is a very simple, and legitimate, mass balance argument. If you have a set amount upwelling, and you restrict downwelling, then you must have an accumulation. That accumulation will continue until an equilibrium in the flow is reestablished. As the THC takes many centuries for circulation, that is the order of time that is required to reestablish equilibrium.
“Pressure IS at least an energy carrier or not much would work in this world.”
But, it is not unique to the atmosphere. Increasing atmospheric pressure does not drive more CO2 to downwell. Increasing overall content of the waters does. Atmospheric pressure is a symptom of the increasing content of the waters, not the cause. More on this point in the next response directly below:
“The atmosphere has everything to do with it as there is no internal CO2 transport within the waterflow from upwelling to sinks.”
Absolute nonsense. There are powerful ocean currents and gyres the world over. Take a look (see graphic above).
“Bart, can you give in detail how CO2 in the surface water level increases, while less is transported down with the sinking waters.”
CO2 laden waters are continually upwelling. If less is transported down with downwelling, then where do you think the excess goes?
“Are you talking about the total volume of water or the CO2 content which have nothing to do with each other?”
Always talking about the transport of CO2. Why on Earth would you think differently?
For reasons I do not understand, my reply simply would not go through. I broke it up into pieces, and they are here, here, and here, along with the graphic of ocean currents.
Bart, I will reply only here, as at last the three parts are coming through…
Increasing atmospheric pressure does not drive more CO2 to downwell.
Bart it gets totally ridiculous, Increasing atmospheric CO2 pressure does drive more CO2 everywhere into every liquid where the partial pressure of CO2 in the liquid is less than in the atmosphere, no matter if the atmosphere is 0.000001 bar above that pressure in the liquid or 3 bar in a Coke carbonatation unit.
All what counts is the pressure difference.
Near the poles the pCO2 in the ocean surface is at about 250 μatm. In the atmosphere it is about 400 μatm, a difference of about 150 μatm. That small difference can push about 40 GtC/year into the deep oceans.
A substantial increase in atmospheric CO2 pressure can push a lot of CO2 into the sinking waters down to the deep oceans…
Absolute nonsense. There are powerful ocean currents and gyres the world over.
Yes there are, but none of them do exchange any substantial amount of CO2 between parcels of their flows, except by mechanical mixing if they meet each other.
Simply compare any CO2 exchange speed driven by CO2 concentration differences with the speed of the ocean flows themselves: 12 orders of magnitude difference…
All substantial CO2 exchanges are via the atmosphere, not between water parcels.
CO2 laden waters are continually upwelling. If less is transported down with downwelling, then where do you think the excess goes?
As repeated at nauseum: into the atmosphere, as there is no internal CO2 transport within the waterflow from upwelling to sinks. If there was no exchange between ocean surface and atmosphere or biopump, exactly the same amount of CO2 would sink as was upwelling, regardless of temperature or atmospheric CO2 pressure.
You simply did not answer my question, which asked how any CO2 can build up anywhere in the ocean surface as with warmer oceans there is more loss of CO2 into the atmosphere at the upwelling and less absorption of CO2 from the atmosphere near the sinks: how does CO2 exactly build up in the continuous waterflow if there is more exported into the atmosphere, less transported from upwelling to sinks and less imported from the atmosphere again?
Always talking about the transport of CO2. Why on Earth would you think differently?
Something to do with the sentence:
it is then resisted by the next layer of ocean, which is tuned to the previous volume of downwelling
CO2 in solution has no volume and the sink speed has nothing to do with the amount of CO2 in the waters, it has to do with density (temperature and salt content), no matter how much CO2 is dissolved…
The thermohaline circulation is about 1000 to 1500 years long so water surfacing now and for the past few hundred years would have been sinking to the depths prior to the MWP and during the Dark Ages of the period around 500 to 1000 AD
At the time of such sinking those waters would have been relatively cold and so would have absorbed a commensurately higher CO2 content.
Currently we have a warmer spell with reduced ocean takeup of CO2 and so the CO2 being brought up by the old water would have a higher CO2 content than ‘normal’ and so could well be contributing to the observed increase.
This is a point I made many years ago in an article about ocean cycles.
Stephen Wilde,
1000-1500 years ago CO2 levels in the atmosphere were 270-290 ppmv. Even with increased CO2 upwelling thanks to the biopump, you can’t reach 400 ppmv, as an increase of let’s say 20 ppmv in the upwelling leads to 10 ppmv extra in the atmosphere, as that equally decreases the CO2 influx at the upwelling and increases the outflux at the sinks…
Why should there now be a sudden, huge increase in upwelling CO2, at exact the same moment and in exact the same ratio as human emissions? Not seen in the past of any ice core, while such an excursion of 110 ppmv in 165 years would be visible in every ice core over the past 800.000 years – be it with a smaller amplitude….
The current warmth reduces CO2 flux from atmosphere to ocean at the sinks whilst high CO2 content at the sources (from the colder Dark Ages) pushes more CO2 into the air assisted by historically high amounts of sunshine into the surface waters beneath the expanded subtropical high pressure cells.
Lets say 20ppm extra in the upwelling and 20ppm reduction in the downwelling adds up to 40ppm compounding over time.
Human emissions happen to be high at a time of active sun and reduced global cloudiness. Mere coincidence.
Ice cores do not seem capable of recording short term variations in atmospheric CO2.
It may be common for atmospheric CO2 to vary from 400 or more to 270 from MWP to LIA and back again without the ice cores tracking such changes.
Due to the different timescales for solar variations and the length of the THC there is also scope for in phase periods compounding each other and out of phase periods offsetting each other.
“All substantial CO2 exchanges are via the atmosphere, not between water parcels.”
Ridiculous. The oceans hold 50X the concentration of the atmosphere.
“As repeated at nauseum: into the atmosphere, as there is no internal CO2 transport within the waterflow from upwelling to sinks.”
As asserted ad nauseum. But, it’s just silly.
“…how does CO2 exactly build up in the continuous waterflow if there is more exported into the atmosphere, less transported from upwelling to sinks and less imported from the atmosphere again?”
Mass balance, Ferdinand. If the same amount is transported in via upwelling, but a reduced amount is transported out via downwelling, then there will be an accumulation at the surface. Reestablishing equilibrium takes on the order of time required for THC turnover.
Why is this so hard for you to understand?
Stephen Wilde,
Sorry too much speculation, little real facts.
Ice core records over the past 1,000 years have a resolution of ~20 years. They can capture a change of 2 ppmv sustained over 20 years, or a one-year peak of 40 ppmv. Thus forget 400 ppmv in the MWP…
That sounds like speculation. Please refer me to evidence that, if ice core records ‘capture’ a change of 2ppm sustained over 20 years, then that ‘capture’ is full and complete rather than partial.
Bart:
Ridiculous. The oceans hold 50X the concentration of the atmosphere.
and
As asserted ad nauseum. But, it’s just silly.
That is just an attempt to divert the attention from the question asked. The water flux is at the surface, largely isolated from the carbon mass in the deep oceans. And you still haven’t answered how the increase in CO2 does happen in any part of the oceans.
Thus my question again and again is how the CO2 molecules can accumulate in any parcel of water flowing from the sources to the sinks when the water is warming everywhere, compared to the situation before the warming.
Thus your answer:
If the same amount is transported in via upwelling, but a reduced amount is transported out via downwelling, then there will be an accumulation at the surface.
is only repeating your theory, but you haven’t explained the mechanism why the CO2 molecules in the sinking waters refrain to go down the drain and do accumulate in the surface somewhere upstream the water flow. Thus enlighten me…
Stephen,
Why would it be partial?
Etheridge e.a. have drilled three ice cores at Law Dome, two at the summit and one more downslope. The two at the summit go back some 150 years in time for the average CO2 levels, the third goes back some 1,000 years.
They have measured the air in the firn from near the surface to the bubble closing depth. They have measured CO2 in firn and ice at closing depth: the same CO2 levels were measured in ice, thus in fully closed bubbles as in the surrounding firn, thus with still open pores, at the same depth. Thus no shift in CO2 levels.
Moreover, there is an overlap of ~20 years (1960-1980) between the ice cores CO2 and direct measurements at the South Pole. All data are within 1.2 ppmv for the same average gas age…
Why would it be complete given the large array of potential influences on the CO2 content of water and air immediately before and/or immediately after closure?
We now know from observations that the CO2 content of the atmosphere can vary from 270 to 400 from the LIA to the current warm period.
What evidence do we have that that change has been or is being fully recorded in ice core samples AND that the full record survives the various processes that continue after closure and only slowly subside over long periods of time following closure.
“The water flux is at the surface, largely isolated from the carbon mass in the deep oceans. “
In the near term. But, over the long term, the whole concentration profile from depth to surface has to re-equilibrate. That is why it is such a long term response, and why in the interim you get effectively an integral response.
“…you haven’t explained the mechanism why the CO2 molecules in the sinking waters refrain to go down the drain and do accumulate in the surface somewhere upstream the water flow”
I simply infer that warmer waters will, in general, want to redistribute CO2 content upward, and that redistribution must occur over the entire depth profile, which will take a long, long time. The evolution could be quite complex. Especially with other considerations, such as suggested at this link.
I will not be able to respond any longer to this thread in the next week. Whatever is left to say, we can pick it up again the next time we meet.
Bart:
In the near term. But, over the long term, the whole concentration profile from depth to surface has to re-equilibrate. That is why it is such a long term response, and why in the interim you get effectively an integral response.
Bart, the integral response in the upwelling of what did sink over the past 165 years is zero. It may integrate up to 3 ppmv in the atmosphere (and then it stops) after full equilibrium between the deep oceans and the atmosphere after all what humans emitted in 165 years is mixed into the deep oceans. That starts after ~645 years from now at the upwelling side.
I simply infer that warmer waters will, in general, want to redistribute CO2 content upward, and that redistribution must occur over the entire depth profile
Which is physically impossible: CO2 follows the water flows and at the polar sinks that is much faster than the eventual redistribution of CO2 within that water flow. All what may happen is that if the THC sinks were stopped for any reason (it happened with an enormous inflow of fresh water at the 8.2 kyear event), then the CO2 level could go up in the atmosphere (need to check if that happened during that event). In all other cases any CO2 transport via the water phase simply sinks with the waters.
The only way that CO2 in any water flux can rapidly change is by exchanges with the atmosphere…
Mod – I have tried multiple times to reply to Ferdinand here and above, but for some reason, they are not posting. I do not know why. Can you help?
“You simply don’t understand anything of basic physical processes that is the problem.”
Quite the contrary, I understand quite well that you have a simplified view that simply does not apply in this world.
“Thus there is no CO2 accumulation in the ocean surface with increasing temperatures, there is an overall decrease of CO2 in the full ocean surface.”
Again, you are living in a static universe. New parcels of CO2 are being released from upwelling waters every second to replenish what is lost, and keep pushing it on upward.
Again, this is a very simple, and legitimate, mass balance argument. If you have a set amount upwelling, and you restrict downwelling, then you must have an accumulation. That accumulation will continue until an equilibrium in the flow is reestablished. As the THC takes many centuries for circulation, that is the order of time that is required to reestablish equilibrium.
Bart,
It seems that WordPress has troubles with the number of reactions…
New parcels of CO2 are being released from upwelling waters every second to replenish what is lost, and keep pushing it on upward.
What you don’t realize is that the parcels of CO2 are contained in parcels of water which move from the upwelling zones to the sink zones. The movement of the parcels of water is so fast that any movement of CO2 is practically negligible in the forward or backward direction. Thus while the waters are simply flowing from source to sink, any loss of CO2 on the road (into the atmosphere) is NOT replenished by the next parcel of CO2 as there is no exchange or buildup anywhere from parcel to parcel. All substantial in or out CO2 exchanges are with the atmosphere.
Again, this is a very simple, and legitimate, mass balance argument. If you have a set amount upwelling, and you restrict downwelling, then you must have an accumulation.
Complelely agreed, except that the accumulation is in the atmosphere, not in the ocean surface…
That accumulation will continue until an equilibrium in the flow is reestablished.
Agreed, but that is much faster than you expect: with only 16 ppmv extra CO2 in the atmosphere per K ocean surface temperature increase the equilibrium is reestablished. That is with only 4 years of human emissions, or 8 years including the current sink rate. The deep ocean exhanges are much too slow to have much influence on that rate…
2hotel9,
A good description of the Thermohaline Circulation or easier to pronounce: THC, is here:
https://www.britannica.com/science/thermohaline-circulation
“Agreed, but that is much faster than you expect: with only 16 ppmv extra CO2 in the atmosphere per K ocean surface temperature increase the equilibrium is reestablished.”
This is the nub of it all. You think the 1.4 yottagrams of the oceans respond virtually instantaneously. That is pure fantasy.
Equilibrium cannot be attained for at least as long as it takes for the THC to circulate. It is physically impossible.
Bart,
This is the nub of it all. You think the 1.4 yottagrams of the oceans respond virtually instantaneously. That is pure fantasy.
The equilibrium is very fast between the ~1,000 PgC in the ocean surface and the ~830 PgC in the atmosphere. Any changes in the deep ocean upwelling are slow and are met with the fast reaction of the atmosphere – ocean surface equilibrium.
What did sink from human emissions probably will not be seen ever back, as that is less than 1% of the total carbon in the deep oceans, thus of near zero importance for the current upwelling rate and the ultimate equilibrium between deep oceans and the surface/atmosphere tandem.
It is only important for the removal of any extra CO2 injection into the atmosphere above steady state between ocean surface and atmosphere. The removal rate is an order of magnitude slower than the exchange rate between atmosphere and ocean surface.
The nub of our discussion is that you don’t understand that CO2 doesn’t accumulate in the ocean surface with warming oceans, to the contrary, the ocean surface gets depleted and CO2 accumulates in the atmosphere.
And you don’t understand that any CO2 pressure increase in the atmosphere -whatever the source- pushes more CO2 into the ocean surface and thus in the deep ocean sinks…
Again, you are making assertions. The rate of change of CO2 to temperature relationship tells us clearly you are wrong. The dynamics are much more complicated than you suggest.
That supports points I made to Ferdinand upthread.
The isotope ratio of 13C/12C will change if one alters the rate of biosphere activity on both land and in the oceans.
More biosphere activity takes up 12C in preference to 13C so more C13 accumulates relative to 12C
Less biosphere activity takes up less 12C in preference to 13C so less C13 accumulates relative to 12C.
If warmer global temperatures result in reduced biosphere activity then less 12C will be taken up in preference to 13C, 12C will increase relative to 13C and the proportion of C13 in the atmosphere relative to 12C will fall.
Could warmer oceans with reduced oceanic biosphere activity be the main reason for the observed fall of C13 relative to 12C ?
http://www.aoml.noaa.gov/phod/soto/gsc/currents.jpg
From NASA via Wiki in the public domain, the Thermohaline Circulation:
The NASA picture of the THC doesn’t show up in my browser, but clicking on the simbol gives the picture at the original Wiki page…
OK, guys, all this tossing about of THC in the thread may be confusing to some, so perhaps y’all should just spell it out. Ya know? For clarity’s sake. Besides, Thermohaline Circulation just rolls off the tongue!
2hotel9,
Sorry, wrong reply button used above…
A good description of the Thermohaline Circulation or easier to pronounce: THC, is here:
https://www.britannica.com/science/thermohaline-circulation
You don’t really “get” humor, do you?
2hotel9,
Sorry, the native language barrier gets in the way…
Just trying to keep the conversation lively!
Bart,
I do think that this is worth pursuing further, so thanks for keeping the discussion going.
I think the key here is to take one piece of evidence at a time. Ferdinand makes a big issue over his theory satisfying all data and (in his view) yours being contradicted in every case. I do not agree, but surely the answer is to look at at each piece of evidence in turn and agree (or not) what this shows. There is a tendency here to jump into explanations (i.e. models) and, for example, to refer to the oxygen balance MODEL without addressing fully the data in respect of d13C. If the explanation fits ALL the data, we do not need to rely on other data to test the hypothesis! Incidentally, the data do clearly demonstrate that the O2/N2 ratio is reducing in a quite amazingly linear fashion (vs CO2) but that is a another story.
The current approach is not the way I see science progessing.
Incidentally, 2hotel9, I have a lot of sympathy with your view. Indeed, I thought, when I started out, that because most views here at WUWT had acceepted the model that atmospheric growth in CO2 was mostly if not entirely anthropogenic, that I would easily be able to cross that off my list of uncertainties and quickly move on the issue regarding the possible impact of increasing atmospheric CO2 on climate. This has not been the case, which is why I am still here trying to understand why the biosphere is only capable of absorbing about a third of the anthropogenic emissions in the longer term, whereas EVERY DAY it seems happy to absorb every excess of CO2 over the background without any problem, regardless of how big or small that is. So, I am still trying to understand what is going on. I fully recognise the complexity of the natural system, but at the same time I see a remarkable consistency in the changes in d13C and O2/N2 that do not seem to be addressed by any of the currently accepted models.
Jim,
My other reaction below is on the wrong place, but here some more thoughts about the O2/δ13C changes.
Most of the diurnal up to seasonal and year by year changes are driven by temperature, where the biosphere is the main reactant.
These are huge changes:
Diurnal: +/- 60 GtC in out (biosphere).
Seasonal: +/- 60 GtC in/out (biosphere); +/- 50 GtC in/out (ocean surface).
Continuous: ~40 GtC permanently flowing between equatorial upwelling and polar sinks (deep oceans).
Year by year: +/- 3 GtC (ocean surface + vegetation).
The diurnal change is locally measurable as a huge change in CO2 levels, especially in forests under inversion, but in general doesn’t reach the bulk of the atmosphere.
The seasonal changes are countercurrent for vegetation and oceans and the global difference of +/- 5 ppmv is mainly from the NH extra tropical forests.
All of the above reactions are directly steered by temperature and are also directly influenced by temperature variability.
What happens if you change the amount of CO2 in the atmosphere? Hardly anything. As the above processes are mainly temperature steered, as long as the temperature changes remain the same, the in/out fluxes largely remain the same. Even 30% more CO2 in the atmosphere has hardly any influence on the diurnal to seasonal amplitude or residual uptake by the biosphere. That is because these processes show little reaction on any extra CO2 in the atmosphere, but a lot of reaction on temperature changes.
The main reaction on pressure changes is in the continuous flux between ocean upwelling and ocean sinks: that process is not only temperature sensitive, but also pressure sensitive: a pressure increase in the atmosphere will reduce the CO2 influx at the “warm” side and increase the CO2 outflux at the “cold” side.
Even so, the removal of any extra CO2 injection (whatever the source) into the atmosphere is of a different order than the reaction on (mainly seasonal) temperature changes: you need a lot of pressure buildup (~110 ppmv) for a relative small sink rate (~2.15 ppmv/year). That is the main reason that human emissions are not completely removed in the same year as emitted.
In short: natural processes react different on temperature changes than on CO2 pressure changes. The largest CO2 changes are seasonal, that is mainly temperature related, hardly influenced by some extra CO2 in the atmosphere. Only with large increases in CO2 pressure, some more CO2 is pushed into oceans and into some more vegetation growth…
Have a good Easter!
Ferdinand
Jim,
Indeed it is partly my own fault: I may give the impression that I am jumping to conclusions too fast, but that is because I have looked at all impossible causes first, before looking at all possible causes.
Take the O2 and δ13C changes in combination with the CO2 increase.
That excludes the oceans as main source of the CO2 increase, as that would increase the δ13C level, while practically indifferent for O2 (except for the solubility coefficient for temperature).
No matter any nice theory that “proves” that the oceans are the source of the CO2 increase, that is physically impossible.
I still don’t have all answers on why the oceans are not the cause, or why a theory can’t be right, but only one observation like the above is sufficient to eliminate the oceans as cause.
So, we are left with either fossil organics or recent organics as source. That can be determined by looking at the oxygen balance. The CO2 release of burning fossil fuels is known with reasonable accuracy, based on sales and burning efficiency. The difference with what is measured is what the biosphere as a whole does. That shows that the biosphere is – at least since 1990 – in average a small but growing net sink. That is confirmed by satellites monitoring chorophyl levels at the surface.
Thus growing biomass is producing O2, taking in more CO2 and by preference 12CO2, thus leaving relative more 13CO2 in the atmosphere, thus again not the cause of the CO2 increase in the atmosphere, neither the δ13C drop.
What is unsure is how humans interfere with the biosphere by land use changes (not included in the above fossil fuel influence). Thus it is possible that the ~1 GtC/year uptake of CO2 by the biosphere in reality is ~5 GtC/year biomass uptake and ~4 GtC/year CO2 release from human destruction of rain forests. Anyway, that doesn’t change the fact that the biosphere is a net sink and not the cause of the CO2 increase, neither of the δ13C drop.
The rest of the evidence like the lags in δ13C drop and CO2 increase between latitudes and altitudes and mostly between NH and SH are additional indications that the low-13C (and zero 14C) additional CO2 source is in the NH, where 90% of the human emissions are. These indications are not perfect, as there are frequent short living disturbances by temperature, El Niño/La Niña, Pinatubo,… and changes over longer periods like the growing uptake by the biosphere, which is already some 10% of the human contribution.
As long as these indications don’t contradict the main drop in δ13C or increase of CO2 somewhere near ground in the NH, one can be confident that humans are to blame (or to thank…) for the increase…
Ferdinand,
You make the absolute assertion that the drop in the C13 isotope form of CO2 in the atmosphere is proof positive that the increase in CO2 in the atmosphere is anthropogenic.
I have found that the more efficient plant growth becomes i.e. the more plant material created from a given amount of photosynthesis the more C13 is incorporated into the plant material and subsequently locked into the soil when the plant dies.
The fact is that higher CO2 makes photosynthesis more efficient and so the reduction in C13 could be a simple consequence of more efficient photosynthesis from a richer CO2 supply. It would therefore say nothing about the source.
Furthermore, it seems that the so called C4 photosynthesis metabolism such as that found in grasses (including food crops such as wheat and corn) takes up far more C13 than so called C3 photosynthesis found in other plant types. Following the agricultural ‘green revolution’ there has been a substantial increase in C4 plants compared to C3 plants.
Maybe your certainty about the observed change in C13 as a source fingerprint for increasing CO2 is misplaced ?
Stephen,
Indeed more plant growth also means more plant decay. That is even measurable in the seasonal amplitude of low level monitoring stations, mainly in the NH where most plants are situated.
From the oxygen balance we can deduce that in the total biocycle (land and sea plants at one side, bacteria, molds, insects, animals,.. on the other side), there is more CO2 uptake than release. Thus rests the question of the change in δ13C as result of better efficiency of all plants and the shift between C3 and more C4 plants.
C3 plants show a discrimination in isotopes of -33 to -24 per mil δ13C (source: Wiki…)
C4 plants show a discrimination in isotopes of -16 to -10 per mil δ13C.
Thus while these two types of photosynthesis show quite huge differences in isotope ratio, when they absorb CO2, that leaves for both far more 13CO2 in the atmosphere as both use preferentially 12CO2 for photosynthesis.
Thus as long as the biosphere is a net sink, that increases the δ13C ratio in the atmosphere, while we see a huge drop in δ13C of the atmosphere and the ocean surface and the biosphere (leaves).
As practically all other CO2 sources are from inorganic materials (oceans, volcanoes, rock weathering,…) there is nothing left that can cause the huge drop in δ13C than human emissions…
One assumes that at some specific level of biosphere activity (photosynthesis) and ocean/atmosphere CO2 exchange there would be a specific, stable C12/C13 ratio.
So, a more active biosphere should increase the proportion of C13 because photosynthesis (in both C3 and C4 plants) takes up C12 preferentially but in fact we see it dropping.
Perhaps the biosphere becomes a less efficient sink for C12 as the climate warms due to increasing size of the subtropical desert areas and a corresponding drop in equatorial biosphere activity.Total global photosynthesis cannot remain the same constantly so maybe it has dropped and now takes up less C12.
The biosphere can still be a net sink but since it is a less active net sink the C13 proportion will drop as less C12 is taken up.
It is a non sequitur to assert that the biosphere has to become a net source to allow a drop in the C13 ratio. Less efficiency or a smaller scale will also do the trick.
Add that to the decline in forests due to human agricultural activity.
Add to that an increase of C4 plants in place of C3 plants.
Add to that any currently unknown or underappreciated processes that affect the C12/C13 ratio by preferring C13.
Less C12 being taken up by such changes would cause C12 to increase relative to C13 so that the C13 proportion would drop as observed.
The mere fact of the observed change in the C12/C13 ratio isn’t proof of anything unless one can specify definitively why the change has occurred. Insisting that it ‘must’ be caused by human emissions is an unwarranted assumprion because correlation does not equal causation.
Stephen,
Over the past 800,000 years, with enormous changes in temperature and resulting changes in the biosphere, the change in δ13C level was ~0.2 per mil between a glacial and an interglacial period.
Natural variability over the Holocene was +/- 0,2 per mil in the atmosphere (resolution 20-40 years). Natural variability in the ocean surface (rapidly following the atmosphere in isotopic composition) was +/- 0.2 per mil over the period 600-165 years ago (resolution 2-4 years). Since then the δ13C level dropped with 1.8 per mil, near 5 times the total natural variability over 800,000 years in a nice ratio to fossil fuel use.
That drop in δ13C (and 110 ppmv rise of CO2) in the atmosphere since ~1850 is the equivalent of burning down 1/3 of all land vegetation on earth, without regrowth.
Thus until you can find an alternative source of low 13C that did do what human emissions did, let us use the working hypothesis that human emissions are the main cause of the drop in δ13C and the rise in CO2…
BTW, if the biosphere gets less effective in discrimination between 13C and 12C, then the δ13C level in the atmosphere would go up, as the (deep) oceans increase the δ13C levels of the atmosphere…
We are discussing the 13C to 12C ratio and not absolute amounts so your points are not relevant.
One does not need to change C13 at all to change the ratio, it is sufficient to change the scale of the preference for 12C and a less energetic biosphere will achieve that.
No alternative source of low C13 is necessary if the preference for C12 declines as in a less active biosphere.
Interestingly the ocean biosphere as regards plankton and algae is more active in cooler waters so there is another possiblity i.e. that the warmer oceans reduce ocean biosphere activity and reduce the C13/C12 ratio from the oceans. The preference for 12C drops so that the proportion of 13C falls relative to the greater amount of 12C left in the air.
As for the glacial and interglacial comparison you are relying on ice cores again which is not good enough IMHO.
Furthermore, a working hypothesis is all you have yet you put it forward as absolute proof.
There is also the problem that I pointed out to you previously. Observations show no surplus of CO2 either above or downwind of centres of human activity yet significant plumes of CO2 downwind of sun warmed waters.
Stephen,
We are discussing the 13C to 12C ratio and not absolute amounts so your points are not relevant.
In this case neither the absolute amounts nor the change in photosynthesis efficiency are relevant.
As long as the biosphere is a net sink for CO2, that would INcrease the 13C/12C ratio in the atmosphere (more efficient with C3 plants than with C4 plants, but both then do increase the 13C/12C ratio), while we see a firm DEcrease. The same for the oceans: any huge release of CO2 from the oceans, or even a huge increase in ocean-atmosphere CO2 cycle would INcrease the 13C/12C ratio in the atmosphere…
That simply excludes both oceans and the biosphere as main source for the CO2 increase in the atmosphere…
That is not right for the reason I gave before.
There must be a ‘normal’ C13/C12 ratio related to the average level of biosphere activity and ocean emission/absorption.I accept that the average would vary over time but that is not relevant here.
If biosphere activity decreases then the tendency for 12C to be absorbed by the carbon cycle as a whole in preference to C13 will also decrease.
That means that there will be more C12 in the atmosphere relative to C13 than would otherwise be the case and the proportion of C13 would FALL.
Likewise for biosphere activity in the oceans and such activity does decline in warmer oceans. In general, cooler waters are richer in organic material.
Stephen Wilde April 16, 2017 at 5:59 am
Furthermore, it seems that the so called C4 photosynthesis metabolism such as that found in grasses (including food crops such as wheat and corn) takes up far more C13 than so called C3 photosynthesis found in other plant types. Following the agricultural ‘green revolution’ there has been a substantial increase in C4 plants compared to C3 plants.
Wheat is C3 as are rice, barley, oats, soybeans etc.
Oops. Wrong way round.
Main point still applies, though.
Friends,
I really have not entered the debate with Ferdinand, basically because I think that whatever the source of the extra CO2 in the atmosphere, I think the net effect of more CO2 in the atmosphere is cooling rather than warming or it is just about nothing. Therefore, imho the debate is perhaps a waste of time.
However, the thought did cross my mind that it is an interesting problem to look at, just because there seems to be so much interest.
There are indications that in earlier times, earth could have had different pressures which means that it would not be fair to go back too far in time to “calculate’ things that we did not really measure. However, by and by, I believe the weight (pressure) of the atmosphere does not change by much, at least when looked at it over the Holocene. If pressure is constant, the problem just reduces to a vessel with salty water (the oceans) in a laboratory (the earth). Analytical chemistry. No need for Henry and his law. We know there are giga tons of carbonates in the oceans. So we have the following equilibriums:
CO2 + 2H2O + cold HCO3- + H3O+ (1)
HCO3- + heat CO2 + OH- (2)
The process by which the CO2 leaves the vessel is mostly when H2O evaporates, i.e. applying UV heat, top to bottom, rather than heat from bottom to top, assuming that heat from the bottom [volcanic action] is constant. Obviously, extra heat from the bottom to top would also affect the CO2 in the atmosphere. The CO2 dissolves when the solution cools down. At this time we realize that most of the CO2 uptake takes places at the poles and the CO2 output takes place near the equator.
According to my own results earth warmed by about 0.012K/annum over the past 50 years, i.e. ca. 0.6K. We notice that this additional heat shifts the equilibrium (1) more to the left and the equilibrium of the reaction (2) shifts more to the right. In both cases, more CO2 ends up from the solution into our lab.
Now, if you can follow this thought experiment, adding CO2 on top of this extra CO2 to the atmosphere [lab] actually would shift (1) more to the right but by an equal portion would it shift (2) to the left. The net effect of adding CO2 to the atmosphere is increasing the HCO3- in the oceans somewhat.
Lastly, true enough, all human and animal waste is acidic. Most of our factory waste is also acidic. 7 billion people making all this acidic waste, which drains into our rivers which end up in our oceans is probably not nothing. Not that I think this is bad: I found the anion of this waste does stimulate life. It is like dung in the oceans.
Considering our simple lab model, my thinking is that the additional acid added to the system directly reacts with the bi-carbonate,
HCO3- + H3O+ => H2O + CO2(g) (3)
We end up with more CO2 in our lab and reduced [HCO3-] in our vessel.
In conclusion: We have 3 factors affecting the [CO2] in our atmosphere positively:
1) More heat from inside, bottom up,
2) More heat from outside, top to bottom
3) More acidic waste water
total 1+2+3 = + 90 ppm CO2 over the past 50 years.
An interesting observation from this short investigation of mine into this problem is that the CO2 that we put up in the air is neutralizing some of the effects of our acidic waste…. Did you get that?
Made me think…
The key bone of contention is how long it takes the oceans to equilibrate to a change in surface temperature. Ferdinand thinks the adjustment is rapid. But, that is pure fantasy. The oceans are immense. It takes a millennium or so just for a THC circuit. Nothing is going to happen rapidly with such a massive heat sink in the mix.
Furthermore, if it did (which it can’t), it would swallow up anthropogenic emissions just as rapidly as it swallowed up the natural emissions. Ferdinand’s conception depends on two impossibilities:
1) That the oceans respond rapidly to temperature changes
2) That the response is different to natural emissions than it is to anthropogenic emissions.
The data show a temperature response exactly as we would expect for a long, drawn out process of re-equilibration in which the rate of change of concentration is proportional to temperature anomaly. It’s just not even a close call.
Happy Easter y’all…
Bart, comments have been delayed with me, too. They’re not getting lost though; they pop up within a couple hours. It seems the longer the comment the more likely that this happens. (and i don’t even comment much)…
Bart, i happen to know that you like religious allegory in the context of climate change. When it comes to deep ocean warming, i used to be a disciple of “brother bart of the immaculate convection”. But then after careful consideration, i became a “born again trenberther”! i’m convinced that all that needs be is a SST that is higher than the equilibrium state temperature for the ocean to continue to warm for centuries. It sounds to me, from your above comment, that you’re presently on board with this. Rightly or wrongly, i think trenberth is one of those assumptions that would be useful to deem true anyway, just to see where it might lead us. NOW, if the oceans are continuing to warm “faster than evah” on the whole (even though SSTs trend flat, that is to say, not rising), then it stands to reason that the ocean on the whole should be continuing to hold less and less CO2. And, as you say, where else has that CO2 to go except into the atmosphere? Regardless of the partial pressure in the atmosphere, a warmer ocean on the whole will hold less CO2, the atmosphere above it being the beneficiary of all that CO2…
Bart,
About 1):
The temperature equilibrium is with the ocean surface only, not with the deep oceans. If the atmosphere would equilibrate with the deep oceans at about 2-4°C, that would result in a CO2 level in the atmosphere of less than 100 ppmv, effectively killing most life on earth.
About 2):
As explained many, many times. Natural processes respond to natural and human CO2 in exact the same way (with only a small difference for the isotopic composition).
The key point is that natural processes respond differently on temperature changes than on pressure changes. The response time for the latter is an order of magnitude slower than for the first with a relaxation time of ~51 years, while the former is responsible for the short residence time of ~5 years.
The one-temperature-process-explains-all theory is proven wrong, as the response to temperature variability (mainly by tropical vegetation) is not from the same process as what causes the slope in CO2 rate of change (vegetation is a proven sink). No matter if the slope is temperature induced or human emissions induced.
Bart,
Some more detail about point 1):
The sinking waters near the poles have a temperature of around -1 to -2°C. That would cool down the deep oceans temperature, if not the earth warmth would help to increase the temperature of the deep oceans within +2 to +4°C.
That is the temperature of the upwelling waters. Thus cooling the ocean surface where these are upwelling within the hot equatorial waters.
Good for us, the sun gives more than enough warmth to keep the whole ocean surface, inluding the cold upwelling waters, at average around 15°C. Any change in the ocean surface temperature is from a change between insolation and outgoing radiation. I don’t think that the heat exchange between deep oceans and ocean surface has much influence on that balance, not even over centuries…
Fonzie –
The “Immaculate Convection” was an irresistible bon mot. And, it never made sense from Trenberth’s viewpoint – it was an excuse for the “pause”, but there was no reason that the pause would have been caused by a sudden diversion of heating from the atmosphere to the oceans.
I think without a doubt that surface heating must eventually propagate to the depths in some measure. I do not, however, consider it plausible that the character changed in 1998, and warmth that otherwise was going into the atmosphere suddenly got shuttled into the oceans instead.
In the past, my comments have done just as you say, eventually reappearing. However, lately, many have been failing to reappear at all, and that has made my responses a bit disjointed.
Fonzie:
Regardless of the partial pressure in the atmosphere, a warmer ocean on the whole will hold less CO2, the atmosphere above it being the beneficiary of all that CO2…
Would be a little difficult with increasing human emissions and increasing deep ocean temperatures releasing more CO2 in the same atmosphere.
Something like 9 GtC/year (human) + 9 GtC/year from the deep oceans = 4.5 GtC/year increase in the atmosphere…
Regardless of how much CO2 is in the deep oceans, (lucky for us) only the surface temperature counts and that increased with 0.6°C, good for 10 ppmv extra in the atmosphere. Humans released 170 ppmv into the same atmosphere and the observed increase is 110 ppmv…
Henryp,
You did forget to mention 4)…
4) Human emissions: +170 ppmv CO2 over the past 50 years.
1+2+3+4 = 90 ppmv over the past 50 years.
1+2+3 = 90 – 170 = -80 ppmv over the past 50 years.
What is going wrong here?
Ferdinand
That is exactly my point. You did not get that?
at given T (global, heat from inside up + outside in) the two chemical reactions (1) + (2) at the going normal (average) pressure and certain pH are in EQUILIBRIUM, meaning if you now add CO2 on top, you disturb that equilibrium. The forces that be will say to you: this CO2 does not belong here. I have to go left or right. This is the constant of the two reactions ITSELF. I am sure you know a little bit about analytical chemistry?
So, to answer your question: your 170 ppms from human emissions have disappeared into the oceans and became bi-carbonate. They do not play any role.
Hence, my conclusion that there are 3 factors. Nature just knows that what we put up there that does not belong there. Like I said, I think the extra bicarbonate from human CO2 that arrives in the oceans does help a bit to neutralize the normal acidic waste that we put into our rivers. That is another chemical reaction (3). The CO2 from that process goes up and depending on the forces that be it will allow this CO2 up in the atmosphere and establish new equilibriums – or not – depending mainly on overall pH, T and P.
Amazing, is it not.
But that is just my opinion/
Henryp,
You need a little more basic knowledge in chemistry than you demonstrate here…
1. CO2 solution in pure water is acidic (pH ~4). CO2 doesn’t neutralize anything, it makes things more acid (or less basic).
2. A doubling of CO2 in the atmosphere (all other constraints the same), gives a similar doubling of free CO2 (thus not of bicarbonates or carbonates) in fresh and seawater alike, per Henry’s law.
That also gives more bicarbonates and carbonates, but not a doubling, as not only (bi)carbonates are formed but also more H+. That lowers the pH and thus the reactions go back to the left.
The net effect is that the new equilibrium is reached at about 10% change in bi/carbbonates for a change of 100% in the atmosphere and if free CO2 in the ocean surface. That is called the Revelle factor.
Thus 90% human emissions remain in the atmosphere, but that is partly removed by deep oceans and vegetation. At last about half human emissions (as mass) stay in the amosphere for longer periods. That is not “nothing”…
3. Nature doesn’t know anything. It just follows pressures, temperatures, etc. for whatever CO2 is in the atmosphere at that moment.
Bart
CO2 + 2H2O + cold HCO3- + H3O+ (1)
HCO3- + heat CO2 + OH- (2)
Almost all warming is natural.There is no man made global warming or at least not comparable or measurable to the natural warming processes.
Looking at my results, I know that earth’s inner core has been shifting a bit, hence I found no warming in the SH, on average. Almost all warming is in the NH. The magnetic north pole has in fact been shifting north east, very dramatically over the past 50-100 years.
As a result, the north pole has been getting warmer, meaning your sink areas where the CO2 dissolves get smaller. This would affect the equilibrium state of the first reaction and I think this would already be noticeable in decades, rather than centuries. Hence, also due to this and other factors, we see CO2 rising in the past 50 years.
Now, true enough, if you add CO2 on top in the atmosphere I am sure some of it would linger a bit. But the equilibriums eventually have to shift back to the point to what they were governed before, hence more bi-carbonate is produced by the extra CO2. This is basic analytical chemistry. Apart from that we also have the biosphere which has increased by about 30 or 40% over the past 50 years so we lose some of that CO2 that we put up before it even comes back to as bi-carbonate.
So, what I am saying: don’t worry about putting more CO2 up. Either it goes for more lawns, more trees or more crops [that we all want] or it goes into the oceans to make bi carbonate. Which is good, because it neutralizes the acidic waste that we put into the oceans.
It is a complicated process, no doubt. I am not a chemist, so I leave that to others to sort out. Whatever the mechanism, it is one such that it produces a long term relationship in which the rate of change of CO2 is driven by temperatures. One must start with that, and work backwards. One must fit the hypothesis to the data, not the data to the hypothesis.
This source may be useful for further investigation:
Bart
Thx.
perhaps, for more clarity in my story, I should have mentioned that my lab is hermetically closed, i.e. a closed vessel with a finite – constant – volume.
you say [quote from ur doc.]:
‘As we burn fossil fuels and atmospheric carbon dioxide levels go up, the ocean absorbs more carbon dioxide to stay in balance. But this absorption has a price: these reactions lower the water’s pH, meaning it’s more acidic.’
As per my summary, the first statement is correct. The second statement imo is incorrect. The extra CO2 that we put up in the air affects both reactions, i.e. the CO2 is converted to HCO3- but it leaves the pH unchanged [because both reactions produce an equal amount of hydronium and hydroxyl ions, – or, per definition, an equal amount of H2O is made -assuming that both reactions of uptake and output are 50-50]
Like I said, the produced bi-carbonate from our burning of fossil fuels helps in neutralizing the acidic waste water that we put in the oceans.
That is my opinion. I am actually collecting my thoughts on this to be able to address it again easily when this subject comes up again. Not that I really think the source of more CO2 in our atmosphere is a bad thing……./
he…heh… more CO2 is better…..
Enjoy your break ! (?? holiday?)
Bart,
This is essentially what happens in the eastern equatorial Pacific Ocean during an El Niño, as far as I understand it. That is: surface water temperatures rise, overlying atmospheric pressures decline, upwelling stops, phytoplankton die off , etc.
And yet, according to CDIAC, despite being able to raise global temperatures significantly and coinciding with increased atmospheric CO2 growth, a major El Niño has no impact on their view of oceanic sequestration of CO2 (it’s a net sink in their model). All the “action” is in the terrestrial biosphere, which is even a (small) net source at times. But then, this is a model-driven analysis where the oceanic sink is derived through various models and the terrestrial sink is simply calculated as total emissions less atmospheric growth less oceanic sink. It is not clear to me (without re-reading their paper) if/how the oceanic biosphere is addressed in their model.
http://i67.tinypic.com/174cnk.jpg
http://i67.tinypic.com/2i3qbo.jpg
Data (2016 Budget v1.0) and full list of contributors can be found at http://cdiac.ornl.gov/GCP/.
Bart,
Interesting work, startification is known from El Niño, where stalling trade winds stops all upwelling and consequently less CO2 releases from the deep oceans / less sinks into the deep oceans.
But the rest of that article says the opposite: that (global) warming and ozone depletion gives more wind speed and thus more upwelling and less CO2 uptake…
Too much models, models, models,…
What is measured is that in the years after the article, the net sink rate relative increased more than the increase in the atmosphere: the “airborne fraction” 2005-2015 got lower. Seems to me that they need far longer data series…
Jim Ross,
While the ocean sinks are based on measurements, terrestrial sinks are calculated from the residual and models. That analysis is confirmed by the oxygen balance, as that shows how much oxygen is produced or used by the biosphere after subtraction of what was used by burning fossil fuels:
http://www.bowdoin.edu/~mbattle/papers_posters_and_talks/BenderGBC2005.pdf
See Fig. 7 in color at the last page.
In principle the oceanic biosphere is included in the oxygen balance, as oceanic O2 simply follows the atmosphere and the solubility of O2 in seawater with temperature. Thus any extra release or uptake from the oceanic biosphere would influence the O2 atmopsheric budget.
Also interesting is that the oceanic variability is small compared to the huge terrestrial variability which is confirmed by the opposite CO2 and δ13C changes.
That also confirms that the variability in CO2 rate of change and the slope of the CO2 rate of change are not caused by the same processes…
henryp April 17, 2017 at 10:33 am
Bart
you say [quote from ur doc.]:
‘As we burn fossil fuels and atmospheric carbon dioxide levels go up, the ocean absorbs more carbon dioxide to stay in balance. But this absorption has a price: these reactions lower the water’s pH, meaning it’s more acidic.’
As per my summary, the first statement is correct. The second statement imo is incorrect. The extra CO2 that we put up in the air affects both reactions, i.e. the CO2 is converted to HCO3- but it leaves the pH unchanged [because both reactions produce an equal amount of hydronium and hydroxyl ions, – or, per definition, an equal amount of H2O is made -assuming that both reactions of uptake and output are 50-50]
Your chemistry is faulty Henry.
Here is the actual sequence of equilibria:
CO2(g) ⇄ CO2 (aq) + H2O ⇄ H2CO3 ⇄ HCO3^− + H^+ ⇄ CO3^2− + 2 H^+
As more CO2 is dissolved more hydrogen ions are produced thus shifting the equilibrium from bicarbonate towards CO2 as shown in the Bjerrum plot below:
My comments in this thread have not been an attempt to prove anything one way or another.
Simply to point out that the certainties expressed by such as Ferdinand are unjustified in light of the complexity of the natural world and our imperfect knowledge of it.
A ‘working hypothesis’ does not represent the objective reality.
Stephen,
A working hypothesis can be used until proven wrong.
Until now, there is no proof that human emissions can’t be the cause of the CO2 increase in the atmosphere.
All the alternative “working hypothesis” I have heard of fail one or more observations. Bart’s hypothesis even violates every observation (that must be a record)…
The observed distribution of CO2 in the atmosphere that I referred you to previously suggests that your working hypothesis is wrong.
Thus your hypothesis fails one or more observations as well 🙂
Humility is a virtue.
Please try to be less ‘certain’ in your approach.
Stephen,
That humans are the cause is confirmed by the lag between NH and SH, both for CO2 and δ13C. That there are wiggles around the trends and lags doesn’t prove that the hypothesis is wrong, only that natural processes interfere (but don’t overwhelm…).
Anyway, the drop in δ13C is a sufficient proof that the oceans can’t be the main cause of the increase, thus Bart’s proof is certainly wrong.
And the oxygen balance excludes the biosphere as the main cause, as that is a proven sink.
So what’s left?
Higher up in the thread you were given observational evidence against the NH leading and the SH following.
Also you were given observational evidence that emissions from human activity centres are not showing excess CO2 amounts either above them or downwind.
I suggested that a drop in oceanic biosphere activity would cause less C12 to be taken up in preference to C13 which would leave more C12 in the air and reduce the C13 proportion as observed.
The cause of the variations in the oxygen balance is also unclear so you cannot use that as definitive proof of anything.
We already know that warmer oceans have lower biosphere activity.
You have a working hypothesis but it is contradicted by certain observations, just like various other current hypotheses.
You are wrong to express the level of confidence that you do.
Stephen;
Absence of evidence is not proof of violation…
The SH follows the NH with a lag that is evidence that the source of low-13C is in the NH,
The lags and the slopes of the 13C decline is different within the two hemispheres, and there is a substantial variability which show that the biosphere also has its influence.
That is not evidence that the biosphere is the main driver of the 13C decline, as the biosphere as a whole (including the oceanis biosphere) is a proven sink for CO2, thus a proven sink of preferentially 12C and thus not the cause of the 13C decline, just the opposite, no matter the shift between C3 and C4 plants.
Other natural sources are all higher in 13C/12C ratio, thus not the cause of the ratio decline.
The OCO-2 satellite can’t directly measure human emissions, thus that says nothing about what happens with human emissions in the atmosphere. Moreover the data show physically impossible CO2 levels over the main oceanic sink areas, so they need better calibration.
The cause of the variability in oxygen balance is very clear, as beside the small change of pure solubility in warmer oceans, all O2 is consumed by burning fossil fuels or consumed/produced by the biosphere,
You have a working hypothesis but it is contradicted by certain observations
Not contradicted, modulated…
that ought to tell you something right there. Because there are some very obvious co2 sources around the planet that are natural sources.
Ferdinand, you say: “The lags and the slopes of the 13C decline is different within the two hemispheres …”
Trouble is, they’re not, at least not to any meaningful degree. Also, it would have to be a 9 year “time lag” to fit the offset.
http://i65.tinypic.com/j97mes.jpg
im Ross,
You are right, only a large lag, no difference in slope…
That may be a matter of near proportional ratio in sink speed of the biosphere.
The CO2 emitted by humans has about -24 per mil , maybe even lower nowadays as there is a shift between coal use (at ~-24 per mil) and natural gas use (at -40 per mil and lower).
Every GtC/year absorbed by the biosphere absorbs preverentially the same -24 per mil as where most of the ancient plants coal was made of (only C3 plants at that time), thus leaving +24 per mil CO2 in the atmosphere. Nowadays less, as C4 plants discrimate less between 13C and 12C than C3 plants, to make things more complicated.
The oceans play less role, as the difference is smaller: average -6.4 per mil for a full cycle in the current atmosphere of -8.4 per mil.
In case of an extra absorbtion by the oceans, that gives an increase of +2 per mil in the atmosphere.
Where is measured is also important:
– Most human emissions are in the NH, near ground level, so is most uptake by plants, but most variability in plant uptake (or even temporarely release) is in the tropics (Pinatubo, El Niño).
The Pinatubo eruption had an interesting side effect: besides a modest effect by temperature, photosynthesis was enhanced as scathering of sunlight by the (sulphate) aerosols in the stratosphere did expose more leaves to light which normally were in the shadow of other leaves for part of the day. That can be seen in the in an extra drop CO2 rate of change in the years after the eruption and the flat, even slightly upgoing δ13C levels…
Anyway, neither the oceans, nor the oceans can be the main cause of the drop in δ13C, as both increase the δ13C levels. But they are the main cause of the less steep drop in δ13C than if all human CO2 remained in the atmosphere…
micro6500
that ought to tell you something right there. Because there are some very obvious co2 sources around the planet that are natural sources.
Something known for decades since the measurements at the South Pole and Mauna Loa started. But that says next to nothing about the balance between natural sources and natural sinks… The latter seems always forgotten by many skeptics: indeed natural sources are huge, but natural sinks are higher: nature shows more sink that source and human emissions are twice the observed increase in the atmosphere, even if that is only 0.01 ppmv/day…
Ferdinand
can you see somewhere the latest results of CO2 in Barrows?
Henryp,
Lots of CO2 and other data at the NOAA carbon tracker:
https://www.esrl.noaa.gov/gmd/dv/iadv/
Choose Barrow on the map (or BRW from the drop down list), carbon cycle gases, time series, in situ data, monthly averages…
The graph pops up and you can ask to download the data…
Ferdinand
CO2 solution in pure water is acidic (pH ~4). CO2 doesn’t neutralize anything, it makes things more acid (or less basic).
Guys
True enough. It’s been a while that I even looked at chemistry, so I saw the OH- in my 2nd equation and thought that it would neutralize the H+ from the equation (1). But to produce the HCO3- it takes the OH- out of the solution, making it slightly less basic.
So, the CO2 from humans has been dissolved leaving the solution a bit less basic. At this point we must realize that the solution that we have is a very strongly buffered solution, with giga tons of carbonates dissolved. So, I am not really worried about the acidity coming from the 170 ppms of CO2 that went into the oceans. You won’t even notice that with a change in pH.
I would be more worried about all the acidic waste from our agriculture and factories which is a lot more than the 170 ppms CO2 from the [total] atmosphere. So, disappointing, but no miracle cure for that waste yet…..
Stephen
My pool seems to get more [green] algae when the water gets warmer. Surely warmer water promotes life?
henryp,
I am certainly no expert in this, but it seems to be very well established that phytoplankton flourish during La Niña due to the upwelling of cold, nutrient-rich waters, most notably off the west coast of South America.
During an El Niño the warm surface waters of the equatorial Pacific spread eastwards, and shut off the supply of upwelling cold waters and the nutrients. This leads to a major die-off of the phytoplankton, which has a major knock-on effect up the marine food chain. This is evident in severly reduced fish stocks, something well-known by fishermen in the region. See here for example:
http://blogs.agu.org/geospace/2016/02/01/13164/
henry wrote, “So, I am not really worried about the acidity coming from the 170 ppms of CO2 that went into the oceans. You won’t even notice that with a change in pH.”
henry, surely you know, right, that scientists have already measured a drop in average ocean pH of 0.1-0.15 since the 1750s?
https://en.wikipedia.org/wiki/Ocean_acidification
Phil.
crackers
Yes Phil., we been over this before, i.e. the errors of my way. Still, I am saying that if we have a vessel with finite constant volume and constant pressure, filled with a buffered carbonate solution, of certain pH and a restricted amount of air on top, then the reaction is kept in equilibrium by the reaction constant. We have two reactions, i.e. uptake and output
CO2 + 2H2O + cold ⇄ HCO3- + H3O+ (1) (mainly at the poles)
HCO3- + heat ⇄ CO2 + OH- (2) (mainly near the equator)
Note that at certain pH, and all things being equal with P and T, if we now add CO2 in the vessel, the natural EQUILIBRIUM is disturbed: reaction (1) will shift from left to right; reaction (2) will shift from right to left. The actual equilibrium is determined by the reaction constant. In both cases the CO2 will be removed and we are left with more HCO3- in our solution and it becomes slightly less basic. Now, remember that there are giga tons of carbonates in the oceans, so you would not even have noticed a change in pH in of the buffer for that 170 ppm that went from the atmosphere into the oceans. You don’t have to worry about that.
Like I said, we do have problems with our waste water; generally all waste water from humans and animals is acidic. Agriculture, factories and mines all produce very acidic water and all of this ends up in the river and ultimately in the oceans. 7 billion people making waste is something to think about.
These are strong acids (sulfuric, phosphoric, hydrochloric, ureic, etc.)
As they enter the oceans HCO3- reacts: HCO3- + H3O+ => CO2 + H2O. (3) A new pH is established. As crackers suggest, the pH of the buffer goes down a bit but I think it is not even 0.1 yet compared to 100 years ago. Anyway, who has records for total alkalinity of the oceans for the past 100 years? As the pH shifts (1) + (2) would allow a bit more CO2 up in the atmosphere, thereby becoming a little bit more basic again, but once again this change is most probably too little to notice.
So to sum up we have the following main factors that affect [CO2] in the air,
[assuming P and V constant, no change in volcanic activity]
1)heat from top to bottom
2) heat from bottom to top
3) acidic waste water
henryp April 18, 2017 at 11:48 pm
Phil.
crackers
Yes Phil., we been over this before, i.e. the errors of my way. Still, I am saying that if we have a vessel with finite constant volume and constant pressure, filled with a buffered carbonate solution, of certain pH and a restricted amount of air on top, then the reaction is kept in equilibrium by the reaction constant. We have two reactions, i.e. uptake and output
CO2 + 2H2O + cold ⇄ HCO3- + H3O+ (1) (mainly at the poles)
HCO3- + heat ⇄ CO2 + OH- (2) (mainly near the equator)
And still you get it wrong!
Your reaction 2 is incorrect, as above it is
CO2 (aq) + H2O ⇄ H2CO3 ⇄ HCO3^− + H^+
Your statement that there is a different equilibration reaction in the tropics that involves OH- instead of H+ is incorrect.
Phil.
I think we are going here into your semantics thing again. Sure, in both [half] equations K is the same, but,,,
e.g. To make a standard solution we boiled the de-ionized water to remove dissolved CO2 and bicarbonate for at least 10 minutes. After cooling down we had to neutralize the solution to pH=7 with a few drops of diluted acid. How would you describe what you were doing:
I think we may assume that all carbonates had been suitably removed in the de-ionizing process.
So by boiling we removed the dissolved CO2. Since we still needed a few drops of diluted acid, this is what [also] must have happened:
HCO3- = > CO2 (g) + OH- (2)
OH- + H3O+ = > H2O. (4)
Unless you did it differently in the USA?
So, I think there is nothing wrong in presenting the equations (1) + (2). The reason why I did it my way was to show you that the extra CO2 in the air is coming from
1) reduced sink areas (arctic)
2) increased irradiation (equatorial regions) at least until the beginning of the new millennium
3) reduced pH of the buffer solution
Go figure why CO2 is higher today then it was 50 years ago.
oh…my….
I made a mistake again.
shoe….
before someone makes a remark again about my [rusty] chemistry
OH- + H3O+ = > 2H2O (4)
ja, ja
I am keeping notes.
Not that I think it is important where the CO2 comes from.
If it is Good it means it comes from God.
Elementary [language]
…..
henryp April 19, 2017 at 9:52 am
Phil.
I think we are going here into your semantics thing again. Sure, in both [half] equations K is the same, but,,,
e.g. To make a standard solution we boiled the de-ionized water to remove dissolved CO2 and bicarbonate for at least 10 minutes. After cooling down we had to neutralize the solution to pH=7 with a few drops of diluted acid. How would you describe what you were doing:
I think we may assume that all carbonates had been suitably removed in the de-ionizing process.
So by boiling we removed the dissolved CO2. Since we still needed a few drops of diluted acid, this is what [also] must have happened:
HCO3- = > CO2 (g) + OH- (2)
OH- + H3O+ = > H2O. (4)
Nothing semantic about it, I’m talking about the equilibria involved in seawater not what procedures you carried out in a lab with boiling deionized water!
This is the sequence that applies:
CO2(g) ⇄ CO2 (aq) + H2O ⇄ H2CO3 ⇄ HCO3^− + H^+ ⇄ CO3^2− + 2 H^+
First CO2 dissolves in the ocean and attempts to maintain the equilibrium defined by Henry’s Law
CO2(aq)=pCO2*3.4×10^-2
The dissolved CO2 reacts with water to form carbonic acid which forms bicarbonate ion which is the dominant species in the ocean (~90% of the total). The equilibrium position of this sequence depends on temperature and pH, formation of carbonate also produces H+ which by Le Chatelier’s principle pushes the equilibrium towards more CO2.
With regard to your lab experiment, when you boil your deionized water you expel all the CO2 and there will be no cations present (so no buffering). If you cooled it down to 25ºC in the absence of air it will be at pH 7, however if you don’t exclude the air then CO2 will dissolve and you’ll end up with a slightly acidic solution. Why your sample became alkaline is a mystery, but CO2 would not do that.
phil.
I think now you have demonstrated that you never even made a standard solution. Must have been below your level of education?
Obviously, after de-ionizing the water stood for a while, ‘airing’, and some more CO2 got absorbed and further down the equilibrium line in the vessel some already dissolved CO2 became bi-carbonate / carbonate etc. due to the reactions that we are discussing.
Hence the need to ‘neutralize” after boiling. Didn’t we use phenolphtalein as indicator to see which way it went? Cannot remember now. These were the early days.
So, ja, it is not the CO2 that did it. It was the HCO3-….
Anyway, my points as to where the extra CO2 in the atmosphere comes from have been made.
henryp April 19, 2017 at 2:08 pm
phil.
I think now you have demonstrated that you never even made a standard solution. Must have been below your level of education?
Obviously, after de-ionizing the water stood for a while, ‘airing’, and some more CO2 got absorbed and further down the equilibrium line in the vessel some already dissolved CO2 became bi-carbonate / carbonate etc. due to the reactions that we are discussing.
Hence the need to ‘neutralize” after boiling. Didn’t we use phenolphtalein as indicator to see which way it went? Cannot remember now. These were the early days.
I’ve certainly made my share of standard solutions.
No problem with this part of your description, the problem is you said that you “had to neutralize the solution to pH=7 with a few drops of diluted acid”. When the CO2 dissolves in the boiled deionized water it produces an acidic solution not an alkaline one which is what you described. Deionized water in equilibrium with atmospheric CO2 at 350ppm and at 25ºC.
This would be the detailed composition
pH [CO2] [H2CO3] [HCO3−] [CO32−]
5.65 1.18 × 10−5 2.00 × 10−8 2.23 × 10−6 5.60 × 10−11
Henryp,
We don’t have (accurate) pH data from a century ago, as the glass pH meters were by far not accurate enough to measure such a small change in pH. But we had other relative accurate measurements, even at that time. The beautiful point in ocean data is if you know three ocean data, you can calculate all the rest. Thus with e.g. salinity, total alkalinity and total inorganic carbon (DIC), you can calculate the pH of 100 years ago.
Modern measurements are colorimetric and have a repeatability of better than 0.001 pH unit. No problem anymore.
That the pH decreases and DIC increases is measured at several stations, the longest series is at Bermuda:
http://www.biogeosciences.net/9/2509/2012/bg-9-2509-2012.pdf
Which shows pH and DIC in Fig. 5
Heat in the deep oceans or the total C mass present have zero influence on CO2 in the atmosphere, only the temperature of the surface has an influence and the difference between sources and sinks in the deep oceans – atmosphere carbon cycle.
Assuming the latter in equilibrium, ocean surface temperature is good for 16 ppmv/K change in the atmosphere, about 10 ppmv since the LIA. That is all…
BTW, Human feces is normally alkaline, urine near neutral…
Ferdinand
your report mentions a change of -0.05 pH over the past 30 years.
I have no reasons to believe it could not be true. I have worked in the surface treatment industry and I know how much acids go down the drain. You would be surprised. Especially in countries where there are no rules, you will find no waste water treatment plants. Because that eats into the profits….Here in the mines we still sit with so much acid, that they still have not decided as yet how to deal with it….. Rain is also acidic. I am sure if you were to check the outgoing rivers for pH you will get a surprise. France became famous for polluting the rivers in your area (Benelux)/. So, like I said, I think most of that drop of 0.05 is coming from our rivers that flow into the oceans. Your report does not exclude that possibility. If you have the time, you could check the pH of your outgoing rivers, for interest sake..
Speaking of mines: you must come down 1km into a gold mine here. Like I did, you will start sweating and you will realize how big that elephant in the room really is. If it moves a little bit – which we know it did from the shift in the magnetic north pole – it could have a major effect. For the arctic in the particular, it means a dramatic decrease in the sink area, which would affect equation (1).
By the way, did you notice the steep drop in minimum T in your area (e.g. last night)??
My results show a drop in Tmin. of ca. -0.014K/annum in the SH compared to +0.024K/annum in the NH (over the past 40 years)
You see what is happening? The data determine my theory. I have to find plausible explanations for the results I am getting.
But I am flexible. Show me actual data and I might believe your theory.
Henryp,
If the pH drop in the ocean surface was from the deep oceans (undersea volcanoes – SO2 – or from warming oceans) or from river inflow, then CO2 would be released out of the ocean surface and increase CO2 in the atmosphere. Thus DIC (free CO2 + bocarbonates + carbonates) in the ocean surface would decrease.
What is measured is reverse: pH drops, but DIC increases, thus CO2 is pressed into the ocean surface from the atmosphere, not reverse…
Data?
Henryp,
See the Bermuda data where the pH graph was:
pH goes down while DIC goes up.
– When the oceans are warming, DIC goes down (the oceans push CO2 in the atmosphere) and pH goes up, because they loose (acid) CO2.
– When the oceans are receiving more acid (volcanoes, river discharges,…) then pH goes down, but DIC goes down too.
– When the pH goes down, while DIC goes up, then the oceans receive more CO2 out of the atmosphere.
Of course, it is a mix of all three, but the 110 ppmv extra in the atmosphere wins the battle…
phil.
You are deliberately trying to confuse issues. Let us go in detail, as otherwise you will never do it right.
I did not say it had been boiled yet. In my case, the DI water would stand in an unsealed large container until it was “used’/ obviously during this time (months rather than weeks) it had contact with air and aeration when the water was let out and as discussed the following reactions took place:
CO2(g) ⇄ CO2 (aq) + H2O ⇄ H2CO3 ⇄ HCO3^− + H^+ ⇄ CO3^2− + 2 H^+ [Phil. (1)]
[isn’t that right?]
After boiling, and cooling in the SEALED container, all the carbonates had been removed, leaving the solution very slightly alkaline. [usually immediate pink colour from 2 drops of pp] . Hence the need to neutralize. Maybe you did it differently and ended up using an alkaline solution to neutralize. Perhaps that is why the norm speaks of neutralization. Maybe you must consider also to rather using my [half] equations (1) and (2) so you don’t get confused about what is happening and why it happens.
That is the end of my lesson for you today.
henryp April 20, 2017 at 12:21 am
phil.
You are deliberately trying to confuse issues. Let us go in detail, as otherwise you will never do it right.
No the confusion is all yours.
I did not say it had been boiled yet. In my case, the DI water would stand in an unsealed large container until it was “used’/ obviously during this time (months rather than weeks) it had contact with air and aeration when the water was let out and as discussed the following reactions took place:
CO2(g) ⇄ CO2 (aq) + H2O ⇄ H2CO3 ⇄ HCO3^− + H^+ ⇄ CO3^2− + 2 H^+ [Phil. (1)]
[isn’t that right?]
So far so good.
After boiling, and cooling in the SEALED container, all the carbonates had been removed, leaving the solution very slightly alkaline. [usually immediate pink colour from 2 drops of pp] .
This is where the problem arises, what is the source of the alkalinity in your water, it was deionized and then had any CO2 removed by boiling so it should be pH 7? An immediate pink color from phenolphthalein says that your boiled, deionized water is pH 9 or so! In any case the result you have has nothing to do with CO2/water chemistry. The choice of phenolphthalein as an indicator implies that you’re going to titrate a weak acid (H2CO3) with a strong base (NaOH), which would be the right thing to do if your water was saturated with CO2 and you wanted to neutralize it, but the boiling means that’s unnecessary.
Here’s a short video showing what happens when CO2 is dissolved in water.
Bear in mind that this is all for pure water samples, seawater with its buffers is somewhat different.
Phil.
so, you have now shown us all in the video that when CO2 dissolves in water it becomes acidic.
So, now in your own words, what happens to the pH of the water when you remove it e.g by boiling it ?
henryp April 20, 2017 at 7:30 am
Phil.
so, you have now shown us all in the video that when CO2 dissolves in water it becomes acidic.
So, now in your own words, what happens to the pH of the water when you remove it e.g by boiling it ?
As I said above it will become neutral, pH 7.
Phil.
So, when CO2 enters the seawater it makes it acidic (pH<7) . But once it leaves the seawater you want it to stay neutral? (pH=7)
seems to me you want it both ways.
It does not happen like that.
I'd rather go with my reaction equations (1) and (2)…..
We were talking about deionized water which you boiled to remove the dissolved CO2 not seawater.
Phil.
so now
please elaborate
what exactly happens in the sea water [where we know the pH is >7] when the CO2 leaves from water to join the atmosphere?
Ferdinand
seems to me the damage to the fruit production in Belgium is due exactly due to the drop of [global] minima.
more CO2 won’t help you a bit…..
henryp April 20, 2017 at 10:01 am
Phil.
So, when CO2 enters the seawater it makes it acidic (pH<7) . But once it leaves the seawater you want it to stay neutral? (pH=7)
seems to me you want it both ways.
It does not happen like that.
It certainly does! It doesn’t stay neutral, it returns to neutral because the species that made it acidic are no longer in solution.
You started off with your deionized pure water, composition at 25ºC:
H2O (55 moles/l), H+ (10^-7 moles/l), OH- (10^-7 moles/l)
In equilibrium with air containing CO2 at 350ppm:
H2O (55 moles/l), [CO2] (1.18 × 10−5 moles/l), [HCO3−] (2.23 × 10−6 moles/l), H+ (~2×10-6 moles/l), OH- (~5×10^8 moles/l), CO3– (5.60 × 10−11 moles/l)
Heat it up and drive out all the CO2 (and HCO3-), the OH- and H+ re-equilbrate to 10^-7 moles/l each and you’re back to pH 7. Which part of that don’t you understand?
phil.
in your own words, please describe the reaction that takes place in the sea water (pH>7) when CO2 is forced out by irradiation in the equatorial regions
Phil doesn’t know that the oceans are alkaline or why 🙂
https://www.physicsforums.com/threads/why-is-sea-water-alkaline.496047/
Stephen, thx.
Did you notice earlier on that I had asked you about algae [in my pool] seemingly getting more abundant when the temperature rises?
La Nina brings up lots of nutrients from below which energises the ocean biosphere. That doesn’t happen in your pool.
In the oceans, colder waters mean a more lively oceanic biosphere.
Henryp,
Phil. was talking about fresh water… If that loses all its CO2, that can’t go up further than pH 7.0.
In the case of seawater: that is an alkaline solution. If you add CO2, pH will go down (a little), if you remove CO2 (by warming), the pH will go up (a little)… For ~370 GtC human emissions since the start of the industrial revolution that is a difference of not more than 0.1 pH unit. Not much to worry: no fish or coral of plankton has problems with that, as these evolved in much higher CO2 levels in the atmosphere…
Indeed we have had two frost nights at a row now. One small tomato plant was killed in my plant box (thought it was aside of the house, so more or less protected, I was wrong…).
Frost nights can happen up to half May here, but in the past decades less frequent than ~50 years ago (you know, global warming…).
The problem this year was that March was unusual warm so that a lot of fruit trees (and vine) were early in blossom. They tried to protect them with fires, spraying water, down wind blowers,… Still a lot of damage, thus less fruit this year,,,
But that is weather, not climate…
Stephen Wilde April 20, 2017 at 12:18 pm
Phil doesn’t know that the oceans are alkaline or why 🙂
Strange then that a couple of days ago in this thread I posted a Bjerrum plot showing the ocean pH to be 8.2 (that’s alkaline in case you didn’t understand that Stephen), and why. Still I guess Stephen is reading comprehension challenged.
https://wattsupwiththat.com/2017/04/07/questions-on-the-rate-of-global-carbon-dioxide-increase/#comment-2479516
henryp April 20, 2017 at 12:14 pm
phil.
in your own words, please describe the reaction that takes place in the sea water (pH>7) when CO2 is forced out by irradiation in the equatorial regions
Nice deflection henry, trying to cover for your complete failure to understand what happens in fresh water by changing the subject. Good luck understanding the ocean.
First of all henry, CO2 is not “forced out by irradiation”. I assume you mean the effect of temperature?
As I said above the process is governed by the following equilibria:
CO2(g) ⇄ CO2 (aq) + H2O ⇄ H2CO3 ⇄ HCO3^− + H^+ ⇄ CO3^2− + 2 H^+
plus H2O ⇄ H^+ + OH^-
and the alkalinity constraint (buffering).
Assuming the system is initially at equilibrium and atmospheric pCO2 isn’t changing (to make things simpler), an increase in temperature will change the Henry’s law coefficient so that some CO2 will outgas to the atmosphere. This will then cause the
CO2 (aq) + H2O ⇄ H2CO3 to shift to the left followed by a shift in
H2CO3 ⇄ HCO3^− + H^+ to the left followed by a shift in
HCO3^− ⇄ CO3^2− + H^+ to the left until a new equilibrium position is attained.
The corresponding change in H^+ will induce a change in OH^- due to Kw = [H^+]*[OH^-]
although Kw for that reaction will also change with temperature (an increase from 25ºC to 30ºC will change Kw from 1.008×10^-14 to 1.471×10^-14).
Good enough for you henry?
Ferdinand Engelbeen April 20, 2017 at 1:10 pm
For ~370 GtC human emissions since the start of the industrial revolution that is a difference of not more than 0.1 pH unit. Not much to worry: no fish or coral of plankton has problems with that, as these evolved in much higher CO2 levels in the atmosphere…
Evolution continues, just because an organism once thrived in past conditions doesn’t mean that their successor species haven’t evolved to adapt to present conditions. This process can be very rapid, the inhabitants of the Tibetan plateau have a mutation that enables them to deal with the low oxygen partial pressure at altitude which has evolved over the last 100 generations!
Phil.,
Plankton (specifically Ehux) has shown that higher CO2 only gives more algal blooms. The 100 generations only needed a few years…
Coral grows adjacent to CO2 fumaroles and oysters/mussels can have a salt and pH range from near acid fresh water to full ocean pH in estuaria…
The problem is that (too) many lab tests were done in conditions which didn’t allow the organisms to adapt: doubling of CO2 in weeks, HCl and other strong acids to give the fast pH drop…
And Ferdinand misrepresents the complexity of the chemical reactions that occur within an ocean biosphere provided with sunlight and nutrients.
There is considerable scientific doubt about the precise details.
Stephen,
The total biosphere, including the ocean surface biosphere, is a net sink for CO2. The ocean surface, including the ocean surface biosphere, is a net sink for CO2. That is all we need to know, no matter that we don’t have all the precise details…
Did you ever stop to think that the ocean is a net sink for CO2 because the mass of the anthropogenic source is “equilibrium” sinking into it?
Fonzie,
There are several lines of evidence:
– DIC increases while pH drops everywhere. That is measured over longer periods in all oceans (except estuaria and upwelling zones). See:
http://www.biogeosciences.net/9/2509/2012/bg-9-2509-2012.pdf
Thus the CO2 flux is from atmosphere into the oceans, not reverse.
– The pCO2 difference over the total oceans is ~7 μatm higher in the atmosphere than in the ocean surface.
See: http://www.pmel.noaa.gov/pubs/outstand/feel2331/mean.shtml
Thus the CO2 flux is from atmosphere into the oceans, not reverse.
– The 13C/12C ratio in the ocean surface closely follows the ratio drop in the atmosphere, not reverse.
– There is no evidence for an increased CO2 emission rate or circulation between deep oceans and atmosphere, directly via upwelling or indirectly via the ocean surface.
– Any temperature increase of the ocean surface re-equilibrates in a few years, with the deep oceans in ~800 years, at ~16 ppmv/K. Good for ~10 ppmv increase since the LIA, far from the measured 110 ppmv increase…
– Oh, yes we have the mass balance. The biosphere is a proven net sink for CO2. See:
http://www.bowdoin.edu/~mbattle/papers_posters_and_talks/BenderGBC2005.pdf
That is not enough to remove the full difference between what is emitted by humans and measured as increase in the atmosphere.
As only oceans and biosphere are fast sources/sinks for CO2, the difference goes where?
So, what is your evidence that the oceans are the cause of the observed increase in the atmosphere?
The biosphere may well always be a net sink for CO2 but that begs the question as to whether at any particular time that sink is running ahead of or behind the creation/release of CO2 elsewhere.
Nor does it deal with the issue of the land biosphere and the ocean biosphere changing their CO2 absorption rates independently of one another.
My current diagnosis is that the ocean biosphere is currently running more slowly than it was due to warmer ocean surfaces inhibiting the upward flow of nutrients to the surface waters. Thus the ocean sink is running less fast and being outpaced by CO2 released by additional sunlight from reduced global cloudiness warming those ocean surfaces so that they hold less CO2. The increase in the land biosphere caused by more CO2 in the air is not sufficient to offset the ocean effect.
When sunlight hits the surface waters there is an initial localised warming of individual water molecules which causes them to release CO2. The warmed molecules then evaporate so the net warming effect overall is near zero but by then the CO2 has been released to the atmosphere and whisked upward by rising more humid air and cannot be readily reabsorbed at the emission site.
Henry’s Law based on average global water temperatures is not a good guide for that effect because evaporation and convection disguise the initial localised warming where the sunlight hits the water.
The effect would be most noticeable beneath the subtropical high pressure cells where most sunlight enters the oceans and that fits with the CO2 distribution charts that I supplied upthread.
That would also reduce the C13/C12 ratio (C12 no longer falls as far below C13 as it did with the more active biosphere) because a slower biosphere gives reduced net impact to the preference of photosynthesis for C12.
FE 4/21/17 12:18a
“So, what is your evidence that the oceans are the cause of the observed increase in the atmosphere?”
i’m not making the claim here that the oceans are the cause of the increase. i’m only making the claim that the oceans being a net sink for CO2 is no indicator that the oceans are not the cause of the increase. Just because the mass of ACO2 is equilibrium sinking into the ocean in a greater amount than the net mass of natural CO2 coming out of the ocean doesn’t mean that the increase is all anthropogenic. — A somewhat similar argument is made by skeptics when they claim that localized vegetation takes out all ACO2. That may be true, but that means that trees are not taking CO2 out of the atmosphere at large. It is the MASS of the ACO2 that has to be accounted for. — In the same way, the mass of each ACO2 and natural CO2 has to be accounted for with the oceans. The mass balance argument does not preclude the possibility that the near entire rise in CO2 is being caused by the mass of natural CO2 coming out of the oceans whilst the near entire mass of ACO2 is equilibrium sinking into the ocean. (yes, all the while that the oceans are a net sink for CO2)…
Now Robert B knows what it’s like to hit a beehive with a baseball bat (let’s see if we can’t push this baby over 1,000 comments)…
Stephen, it seems like three things may be driving a lower C13 ratio. Firstly, a warmer world means a lower C13 ratio (for whatever reason). Since we really don’t exactly know the temperature of, say, the MWP, we can’t really extrapolate what the ratio should be today. Add to that a simple dilution of the ACO2 source since the industrial revolution and we have a second reason. (a “simple” dilution not being so simple because of the first reason) And lastly, that thing called deforestation. One has to wonder about the total impact, not only of a loss of trees, but the potential of the growth of trees since there are fewer of them then there otherwise would be. Seems difficult to come to any definitive conclusions based on C13 ratios…
afonzarelli commented
>> Firstly, a warmer world means a lower C13 ratio (for whatever reason). <<
why?
Warmer ocean surfaces have less biosphere activity since the warm layer at the top inhibits the delivery of nutrient rich water from below.
At a given level of biosphere activity there will be a specific C13/C12 ratio.
If one then energises that activity then C12 will fall relative to C13 due to the preference for 12C in photosynthesis i. e. the amount of C13 relative to C12 would rise.
If one reduces biosphere activity then, instead, C12 will rise relative to C13 because the preference of photosynthesis for C12 will have reduced impact. i.e. the ratio of C13 to C12 will fall, as observed.
So, one can get a fall in the C13 to C12 ratio from a reduction in ocean biosphere activity resulting from warmer ocean surfaces.
Fonzie,
We have ice cores with reasonable resolution (~20 years over the past 10,000 years) which show a small +/- 0.2 per mil δ13C variability in the atmosphere due to temperature variability. We have coralline sponges with a high resolution (2-4 years), which show the same variability between 600-170 years ago in the ocean surface. Since then there is an enormous drop in both of near 2 per mil in ratio to human emissions…
Land use changes by humans is included in the net uptake by the biosphere, as that is based on the oxygen balance: still a net uptake of ~1 GtC/year by the biosphere, while humans may emit ~4 GtC/year from land clearing. Thus the biosphere increased its uptake by ~5 GtC/year. That increases the δ13C level in the atmosphere, but we measure a huge drop in δ13C, despite that the earth is greening by more CO2 and higher temperatures…
The various possible models presented above as explanations for the reduction in atmospheric δ13C in CO2 are all very interesting, but there is one requirement that must be met by any hypothesis: it must match the observations. These show that the reason for the drop in δ13C is that the incremental CO2 has an average δ13C of -13 per mil. As this is below the current atmospheric level of about -8.4 per mil, the atmospheric level drops as more CO2 is added.
The key point, however, is that the data show that the average content is a constant, while short-term fluctuations correlate primarily with ENSO (plus some influence by volcanic activity).
http://i64.tinypic.com/2qlwg42.jpg
Jim Ross,
The only reason why there is a seemingly constant addition of low-13C at apparent -13 per mil δ13C is because human emissions increased with a rather constant ratio over time. That makes that the increase in the atmosphere also increased linear over time and thus the net sink rate.
That makes that the increase/emissions ratio (the “airborne fraction”) remained more or less constant over time, only influenced by the short-living temperature influence on mainly (tropical) vegetation.
If human emissions remained constant at half the current emissions, there wouldn’t be any further increase of CO2 in the atmosphere, neither a further δ13C drop, as the latter is the result of human emissions, diluted by the ~40 GtC deep oceans – atmosphere CO2 circulation.
As the biosphere as a whole is a net producer of oxygen, it is a net sink for CO2 and preferentially 12CO2, thus not the origin of the δ13C drop, just the opposite. All other known (huge) CO2 sources are higher in δ13C than the atmosphere…
NASA wants to terraform Mars. To do this, they want to build factories that introduce methane into the ‘atmosphere’ in order to raise the temperature enough to allow enough CO2 to outgas from the surface such that they may start to grow plants.
“…raising the temperature in an atmosphere increases the vapor temperature of CO2 meaning that more solid CO2 will then evaporate from polar and global regolith (Zubrin, 1996). If the polar and global regolith hold CO2, raising the atmospheric temperature by only 4K (i.e. with greenhouse gases or an orbiting mirror) ultimately leads to an increase in the amount of CO2 outgassed… (Zubrin & McKay, 1997).”
Does this not show that NASA believes a rise in CO2 levels follows a rise in temperature, and not the other way around?
hebgb,
The difference with Mars is that the earth is a water planet, where in the past few million years a quite linear equilibrium between temperature and CO2 is seen of about 16 ppmv/K. Not by coincidence what the change in CO2 solubility in seawater is for a change in temperature per Henry’s law…
Thus a warming of less than 1 K since the LIA is good for some 10 ppmv extra in the atmosphere, not the measured 110 ppmv increase, while humans emitted 170 ppmv CO2 extra in the atmosphere over the same time span…
“The difference with Mars is that the earth is a water planet…”
Do we know that Mars isn’t – re: permafrost?
hebgb,
CO2 doesn’t dissolve in ice…
If it gets warmer, some bacteria on earth start to decay organics and produce CH4 and CO2, but I don’t think that there are much organics – and bacteria on Mars. Although, you never know…
No, but CO2 saturated water does freeze.
Anyhow, NASA seems to think there is quite a lot of CO2 trapped in Mars, and methane, so organics on Mars is not so far-fetched… not to mention the fact that the whole planet is covered in rust (oxidization.)
But this has little to do with my question; so I re-iterate: Does this not show that NASA believes a rise in CO2 levels follows a rise in temperature, and not the other way around?
Guys
I have a question for all of you!
It seems the sublimation temperature of CO2 lies at -79.5C
http://iopscience.iop.org/article/10.1088/0508-3443/17/3/312/pdf
Now, I am thinking that, at the poles, in winter, the temperature can go below that? Doesn’t that mean that the dry ice will just fall out the sky and get buried into the snow [that will cover it]?
No, we had a long discussion about that a couple of years ago, and in fact it’s why a certain person was banned from here (because of his aggressive attitude in the discussion). You need to look for the triple point of CO2 on the phase diagram and you’ll find that the partial pressure of CO2 is so low that the sublimation point on earth is a much lower temperature than exists here.
https://wattsupwiththat.com/2009/06/13/results-lab-experiment-regarding-co2-snow-in-antarctica-at-113°f-80-5°c-not-possible/
hebgb,
If you put a bottle of Coke in the freezer, and the bottle is not strong enough, there is a high possibility that the bottle explodes, as with freezing all CO2 is expelled out of the ice into the small space above the liquid/ice…
Anyway in any solar system, CH4 and CO2 are well present, water is far less. That is why the possibility of life is quite low for most of any planet: either too cold, to hot (or both by lack of atmosphere or too slow rotation), only traces of water (Mars),…
NASA believes in the (relative) strong warming effect of CH4 (which I do too). Thus the addition of methane by humans can increase the average temperature on Mars and that may set more frozen or captured CO2 free, which may make Mars inhabitable for (earthly) plants. Thus it is both ways…
Henryp,
That sublimation is at 1 bar CO2 pressure (100%) in the atmosphere. At the much lower CO2 pressure in the atmosphere, all CO2 sublimates already at much higher temperatures.
If you want the reverse to freeze 0.0004 bar CO2 out of the atmosphere, you need much lower temperatures.
Compare it to water: boils at 100°C, then all water evaporates, Cool it down, and water will condense: completely if it is 100% water vapor, but if it is only a small percentage as water vapor in air, you need (much) lower temperatures to condense more water and you even need a cold trap at -70°C to condense almost all of it out of the atmosphere…
Phil.
So what you are saying is that there is nothing wrong with my equations:
at the poles,
CO2 + 2H2O + cold HCO3- + H3O+ (1)
and in the equatorial regions
HCO3- + heat CO2 + OH- (2)
at the given current pH of seawater……
I thought as much! You are just making things difficult…
No I’m not saying that, the same equilibria apply in the Arctic and Antarctic seas as in the tropics, the only change is the position of the equilibrium. If that’s too difficult for you to understand……
Phil.
I noted you had to bring in H2O = H+ + OH-
to show the hydroxyl coming from the splitting of the bicarbonate due to heat
That reaction is incorrect. H+ as such does not exist …
Whether you write it as H+ or in the hydrated form is immaterial the reaction is the same, water dissociates and the relative concentrations are determined by Kw. The bicarbonate doesn’t split, it reacts with a proton to form carbonic acid:
HCO3^− + H^+ ⇄ H2CO3 ⇄ H2O + CO2
Your reaction 2 is a fiction.
My reaction (2) was a summary of your reactions, summing up the net result, making it less complicated to understand…..
You honestly don’t get that?
Anyway, thx for this interesting discussion. Always is like a chess match with you but keeps my brain going///…
“Anyway in any solar system, CH4 and CO2 are well present,…”
False, and off-topic.
I appreciate the effort Ferd, but please stop.
.
From the article: “That changes in sea surface temperature would have an effect on CO2 levels is plausible…”
Apparently, not just plausible. If NASA is basing its future Martian terraforming around the principle that a rise in temperature will lead to an outgassing of CO2, and that they have been leading the charge in alarmist circles that it is the other way ’round here on Earth, doesn’t that make them hypocrites, and shouldn’t someone call them out on that? It seems to me to be an easy way to challenge the misconceptions they are laying on the public and to get them, once and for all, to tell the world THEY are full of hot gas.
Who needs M. Mann at congressional hearings? Just get a guy from NASA on tv and ask him two questions.
Problem solved, carbon pricing scrapped, globalist ‘greens’ castrated, and Holdren and all his eugenics-lovin’ buddies like Al Gore and Bill Gates and Bill Nye, discredited. Maybe CERN will stop wasting billions in aerosol research and get back to work making time machines and supra-luminal-speed spaceships and such. If they could get that done, we wouldn’t need to limit ourselves to one world.
Then again, maybe the universe would be better off without us.
hebgb
there is no man made global warming
ergo
more methane or CO2 or more whatever does not change that
Your observation that we should not be here it utterly ridiculous. You are here. You are here on earth for a purpose. I just wrote something about that today////
http://breadonthewater.co.za/2017/04/21/creation-or-co-incidence/
Hebgb,
You still need to make a differentiation between what happens on earth with CO2 dissolved in the oceans and what happens with frozen/absorbed CO2 on Mars…
Temperature of the oceans gives an equilibrium between CO2 in the atmosphere and in the oceans. That equilibrium shifts with 16 ppmv/K, according to Henry’s law. That is all. The current atmosphere contains 400 ppmv, that is a pressure of 0.0004 bar.
On Mars, CO2 is 97% of the atmosphere, but the total atmospheric pressure is only 0.006 bar.
Thus a 4°C increase of the ocean temperatures on earth (that will need many millennia…) will give you only 0.00046 bar CO2 and no measurable increase in total atmospheric pressure, while 4°C on Mars may sublimate enough solid CO2 to double or triple the CO2 and total atmospheric CO2 pressure.
If that will be enough to grow plants remains to be seen, but you can try that out with plants in the same low pressure / high CO2 levels here on earth…
Phil.
Ferdinand
THX!
this is also what I understood from the link
I just wanted to have confirmation from at least 2 people.
Ferdinand
you said
That sublimation is at 1 bar CO2 pressure (100%) in the atmosphere. At the much lower CO2 pressure in the atmosphere, all CO2 sublimates already at much higher temperatures
Henry says
you meant lower temperatures?
Sorry Henryp,
Indeed lower temperatures…
Here’s the phase diagram:
It only extends down to 1000ppm, but basically it shows that you can only get solid CO2 at temperatures below -135ºC, at ~400ppm you’d need to go much colder. At temperatures above that the only stable phase of CO2 that can exist on earth is the gas phase.
@HenryP
Sorry, I don’t believe in fate/destiny/purpose… very unscientific.
“Life does not come into existence from ‘itself’….” Just ’cause we can’t do it, doesn’t mean it can’t be done.
If you believe in some paternal omnipresent sky faerie (you have every right to,) I can’t take anything you say seriously.
@Ferd
It’s the parts that come before one of these —> ? <— that interest me.
IDGAS about Mars.
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