CO2 in the air, CO2 in the seawater

Guest Post by Willis Eschenbach [See updated graph]

Inspired by some comments on another thread, I decided to see what I could find in the way of actual measurements of the amount of CO2 in the surface layer of the ocean. I found the following data on the Scripps Institute web site. What they did was drive around the ocean on four different cruises, measuring both the atmospheric CO2 levels and at the same time, the amount of CO2 in the surface seawater. Figure 1 shows those results:

scatterplot sst vs co2 scripps allFigure 1. All air-ocean simultaneous measurements from four Scripps cruises are shown as blue dots. The horizontal axis shows sea surface temperature. The vertical axis shows the difference between the CO2 in the overlying air, and the CO2 in the water. The red line is a lowess curve through the data. The paper describing the Scripps data and methods is here.

Now, I have to say that those results were a big surprise to me.

The first surprise was that I was under the impression that there was some kind of close relationship between the atmospheric CO2, and the CO2 in the surface seawater. I expected their values to be within maybe 5 ppmv of each other. But in fact, many parts of the ocean are 50 ppmv lower than the CO2 concentration of the overlying air, and many other parts of the ocean have 50 ppmv or more of CO2 than the CO2 in the air above.

The second surprise was the change in not only the size but even in the sign of the trendline connecting temperature and CO2 (red line in Figure 1). Compared to the CO2 level in the air, below about 17°C the seawater CO2 decreases with increasing temperature, at a rate of about -2 ppmv per °C.

Above about 17°C, however, the seawater CO2 content relative to the air increases fairly rapidly with temperature, at about +4 ppmv per °C.

To describe the situation in another way, when the water is cool, it contains less CO2 than the overlying air … but when the water is warm, it has more CO2 than the overlying air.

Say what? I gotta confess, I have little in the way of explanations or comprehension of the reason for that pattern … all suggestions welcome.

w.

[UPDATE] By popular request, here is the same data, but in absolute rather than relative units and without the lowess curve.

scatterplot sst vs co2 scripps all no delta

 

Figure 2. As in Figure 1, but showing the CO2 content of the surface seawater directly. Atmospheric CO2 varied very little during the time of the measurements.

My main question in all of this is, how does the CO2 content of the seawater get to be up to 100 ppmv above the CO2 content of the overlying air? It seems to me that the driver must be biology … but I was born yesterday.

Regards,

w.

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197 Responses to CO2 in the air, CO2 in the seawater

  1. lemiere jacques says:

    CO2 roduced by biomass …rain…evaporation…

  2. ronald says:

    Can it be a agw survey? Cold water absorbes CO2 and warm water let it go by out gassing. It looks to me that someone wants to let look to work the other way to help agw.

  3. Juan Slayton says:

    Are we assuming equilibrium? The air temperature is constantly changing, I would presume the water temperature also, though less so. CO2 levels may also be changing. Would be nice to have a ‘dynamic’ record from a single location, showing response to temperature or CO2 change.

  4. lemiere jacques says:

    oh sorry and wind…some co2 arrived from elsewhere land for instance…so you can see a dynamical process…and some saturation too…quite complicated indeed for sure you can’t see it like an equilibrium…
    well and the water at the surface exchange a bit withe the water underneath…

    you should try to figure out how co2 concentration vary in the atmospheric surface layer how it varies in the ocean surface layer… temperature paly a role..

    another point…temperature of what? air of temperature?
    it they are fifferent it is weird to assume that there should be some kind of equilibrium.

  5. johnmarshall says:

    You missed most of the reaction. Sea water is an ionic solution and dissolved CO2 continues reacting to form bicarbonate ions, which increase the pH so maintaining the pH balance, and this bicarbonate ion is used by animals to form shell and skeletal frameworks. Without this further reaction corals would not grow. So the takeup of CO2 depends on planktonic life, the more active this life the more bicarbonate is used then the faster the CO2>bicarb reaction continues. Dissolved CO2 remaining in the water is used bu planktonic and other plants to photosynthesize. These chemical reactions speed up with temperature rise.

  6. Juan Slayton says:

    A lot of photosynthesis goes on in the ocean. Could the dip from 5 to 25 degrees reflect favorable conditions for photosynthetic growth?

  7. Julien says:

    It would seem like the correlation between higher CO2 and higher temperatures would be only verified for seawaters above 25c? Alternatively, another way to look at it, is that the radiative equations only work when the angle formed by the sun and the surface close to perpendicular: Global warmist assume a flat earth as a greenhouse, they may underestimate the fact that without direct sunshine there is no greenhouse effect going and temperatures and sinking rapidly.

  8. Macha says:

    Relative difference is not the same as absolute. Warmer water can absorb and hold more CO2, than cold. The rate of change I more a question of kinetics.

  9. martin brumby says:

    The vast majority of their dots are for sea surface temperatures greater than 20ºC.
    Perhaps the cruises in oceans where this was the case were more popular with the psyentists than those trawling around oceans with temperatures below 10ºC?
    Or maybe the latter group just kept warm and cosy below decks?

  10. “To describe the situation in another way, when the water is cool, it contains less CO2 than the overlying air … but when the water is warm, it has more CO2 than the overlying air.”

    When water is cool CO2 flows from air to water – net absorption.

    When water is warm CO2 flows from water to air – net release.

    ” many parts of the ocean are 50 ppmv lower than the CO2 concentration of the overlying air, and many other parts of the ocean have 50 ppmv or more of CO2 than the CO2 in the air above.”

    Looks like there are mechanisms in play that make the application of Henry’s Law rather hit and miss.

    Most likely the CO2 exchange rate varies as many other factors such as internal ocean movements and winds in the air interfere with the exchange process.

  11. TimC says:

    Purely from eye-balling the data, the Lowess curve line at SST 0. Without this cluster a normal linear regression would seem to fit well (don’t have time to do it right now) crossing the OSco2-Aco2 axis at about SST = 18 and with d(OSco2-Aco2)/dSST =1 approx.

  12. TimC says:

    Sorry – the first sentence of my post above should be: Purely from eye-balling the data, the Lowess curve line at SST less than 5 seems to rest essentially on the small data cluster at around SST = 2, OSco2-Aco2 greater than 0. Without this cluster …

  13. The vast majority of CO2 in the oceans is in the form of bicarbonate. Only a tiny fraction is in the form of the dissolved gas, which is what this paper is measuring. The inorganic exchange between dissolved gas (as in soda water) and bicarbonate is governed mostly by the reaction:
    CO2 + H2O —> HCO3- + H+
    You can see the H+ lowers the pH. There is a huge organic component to this process as well. We escaped the fate of Venus in large part due to the formation of calcium carbonate by marine organisms, that pulled nearly all of the original CO2 out of the atmosphere to create limestone, the abundance of which is evident to anyone who has looked at rocks around the world.

  14. Mike Edwards says:

    The most straightforward observation I can make regarding the scatterplot is that the data looks rather inhomogeneous – clusters here and there and gaps between them. To me, this would indicate that other factors are at play here beyond CO2 and temperature.

  15. Dudley Horscroft says:

    Just possible that at close to zero (0 to 5 C) CO2 in air and water are in equilibrium – not much happening. As the water warms, the amount of CO2 in water decreases, as one would expect. Further, as temperatures approach 10 to 15 C plant life does well and it reduces CO2. However, past 17C, it is better for animal life, and this eats the plants and exhales CO2, so increasing the amount of CO2 in the sea water.

    BTW – we “exhale” via our lungs – does a fish “exhale” via its gills – if not, what is the correct term for “a fish getting rid of CO2?”

  16. Bloke down the pub says:

    In areas with lower temps the sea water might be down-welling thereby taking the CO₂ below depths where the measurements were being taken.

  17. Bill Onesty says:

    My only response is – What? You would draw a TREND line? Through THAT? REALLY?

  18. Keitho says:

    It almost looks as though the CO2 rising from deeper down is encountering a choke at the surface slowing down release. Perhaps the surface tension is doing it. But it seems to result in a CO2 rich zone close to the underwater surface with only a slow release to the atmosphere.

    Interesting finding W

  19. Claude Harvey says:

    In summary: You can’t cough it up unless you have more of it.

  20. Dudley Horscroft says:

    Unfrozen Caveman said:

    “We escaped the fate of Venus in large part due to the formation of calcium carbonate by marine organisms, that pulled nearly all of the original CO2 out of the atmosphere to create limestone”.

    Circular reasoning. If the runaway greenhouse effect were valid, with all that original CO2 in the UnfrozenCavemanMD said:

    “We escaped the fate of Venus in large part due to the formation of calcium carbonate by marine organisms, that pulled nearly all of the original CO2 out of the atmosphere to create limestone”.

    Circular reasoning. If the ‘runaway greenhouse’ effect were true, with the original atmosphere largely of CO2, temperatures would be on average above boiling point of water, there would be no oceans – no liquid water in which marine organizms could exist, and which could turn the CO2 into limestone. These marine organisms would most likely have been very happy with an ocean temperature perhaps 8 to 10 degrees C above present – which would probably be the likely figure if the atmosphere were 60 – 90% CO2.

  21. Nylo says:

    Thanks a lot for this article Willis, it made me think and I love it when new data or ideas make me think.
    I had to reconsider everything I know, even regarding outgassing, as it is at odds with the outgassing of CO2 from the ocean that supposedly happens when temperature increases. Is it really true?
    Well, of course it is. What perhaps may be not so true, is that this outgassing affects the atmospheric concentration of CO2. There will be more CO2, yes, but I’m guessing that the oceans will NOT ONLY release CO2. There must be other gasses disolved as well. So it outgasses CO2, and maybe O2, N2, Argon… as well. So concentration of CO2 in the atmosphere MAY NOT change as a result of the outgassing.
    But wait! We have paleoclimatic records showing more atmospheric CO2 when warmer! Isn’t that proof of CO2 release by the oceans? Well, it may perhaps be proof of more CO2 PRODUCTION in the ocean, increasing the ammount of CO2 that is dissolved in the water just because of biological productivity (more O2 consummers than CO2 consummers), making the concentration greater than there is in the atmosphere as your calculation here has showm… and then by outgassing, transfering some of this difference in CO2 concentration to the atmosphere.

    That’s the only explanation I can think of right now. But it brings interesting conclussions if it happens to be true, doesn’t it? To begin with, all the story about ocean acidification crumbles. Ocean acidifies, yes, but not necessarily because of our emissions, but because of its own biological processes as a result of the warming… And part of the accumulated CO2 in the atmosphere would have been released by the oceans, not us.

  22. Nick Stokes says:

    Willis,
    I don’t think the water measurement reflects concentration of CO2, and I’m sure it isn’t ppmv of water. It’s described in your link as pCO2, which would be the partial pressure of CO2 in equilibrium with the seawater.

    In that case, there’s no particular expectation about variation with temperature. With no flux, it would be zero at any temperature. What it does reflect is which way CO2 is moving.

    On that basis it should indeed be higher in warm water, because that is thought to be a region of degassing. So pCO2 must be higher below the surface. CO2 moves down a gradient of pCO2.

    In fact, though, it would be very seasonally dependent. All sea water loses CO2 toward summer, and takes it back before winter. So timing of the readings would be important.

  23. Dudley Horscroft says:

    As has been pointed out many times, the more the CO2, the less the additional effect of ‘greenhouse warming’. The additional temperatures would be due to the increased internal heat of the earth escaping to the surface, and increased heat as a result of a turbulent atmosphere. Those good with figures can calculate the surface air pressure if all the CO2 in the rocks in the form of chalk, limestone and marble were free in gaseous form, and what the surface air temperature would be if the atmosphere were turbulent, and the temperature on the surface were due to compression of downward moving air. And of course, in those early days, there would be plenty of vulcanism adding heat at ground level.

    Remember that much of the CO2 was removed from the atmoshere not so long ago – the chalk was laid down in the Cretaceous. Before that what was the amount of CO2 in the atmosphere, and what was the surface temperature?

    I apologize for the previous post – the start of my comment disappeared, so I wrote it in again, and then found that the end had been disappeared. So I chpped it and found that the end was still on my clipboard, and put it here.

  24. François says:

    Five years of measurements, fifty years ago, with the instruments available then. I am impressed.

  25. Bob Greene says:

    So, according to that plot when I pop the top on my barley pop I will get more CO2 as it warms up and it shouldn’t go flat faster standing at warmer temperatures? I’m not sure what they were measuring but the concentration of CO2 (all forms) is inversely proportional to temperature. CO2 chemistry in water is a bit more complicated so if they were just measuring dissolved CO2 they might have gotten strange results. You need to know pH and total carbonate also. http://www.soest.hawaii.edu/oceanography/faculty/zeebe_files/Publications/ZeebeWolfEnclp07.pdf

  26. Sera says:

    There is a natural carbon-dioxide cycle during the year- look at the months (of the year) that the data were taken. I would expect higher concentrations during the fall/winter, and lower concentrations during the spring/summer.

  27. geran says:

    Interesting data, for sure. Several have mentioned photosynthesis, and I agree that might be a huge factor. It would be interesting to see the concentrations versus time of day (or even better, sunlight intensity) to look for the correlation to photosynthesis.

    The correlation to temperature, demonstrated by the scatter plot, appears to be opposite of what I have always heard. That is, the “outgassing” appears to increase at colder temps. WUWT?

  28. Dodgy Geezer says:

    …The first surprise was that I was under the impression that there was some kind of close relationship between the atmospheric CO2, and the CO2 in the surface seawater. …

    Alas, Willis, you have been infected by IPCC reasoning. The idea that there are only a few big variables and they interact with each other in a simple manner is what you say when you are a political advisor hoping to persuade a politician.

    “Yes, Mr Prime Minister – if you enact this law you WILL get more votes…”

    In reality we have two domains here, the sea and the air. Each has a set of pressures and balances which determine the local CO2 concentration. At the point where they touch – the sea surface, they probably interact with one another. But how important that interaction is compared with their own internal driving variables… who knows?

  29. Richard Graves says:

    I like to make soda water. Thinking very cold water would make bubblier soda that’s what I tried. Results not good! Then I tried water from tap around 20C. Result nice bubbly sodas. Seems the warmer water absorbs more CO2 more easily. Its been bothering me why?

  30. Macha says:

    But consider the Y -axis is difference , so 10ppm ocean CO2 – 15ppm air CO2 can be in cold water when gas is less absorbed, and 40ppm ocean – 35ppm can be for warm water. Yet each has opposite sign. I would also like to see gross CO2 on y axis.

  31. chris moffatt says:

    Where did they do their sampling? Most of the plot points are where SST is >25C (77F). Seems to me to be hardly a representative sampling of the world’s oceans.

  32. Greg Goodman says:

    Oof, where to start.

    first you need to change compatible units before subtracting. Ocean measurements will be partial pressure as someone else comments. ppmv can be converted to atm. part. pressure. Then you can subtract and the difference is physically what drives exchanges.

    As for the data I see several concentration of dots that seem to suggest some very difference relationships are being dumped together. You probalby need to do some geographic splitting of the data to separate things before doing and modelling and fitting exercise.

    I see:

    1) about 27 deg. a huge range of variation that is dependent of SST (straight up and down).

    2) Between 17-24 a nice linear section in the middle.

    3) from 8 deg down through a min at 20 and back up throught the most dense region a parabolic curve. This may be mental pattern spotting or some real grouping that can be isolated by geography or latitudinal grouping of data.

    4) Lots of loops that will probably be clearer if you join the dots rather than doing a scatter plot. Such loops indicate phase relationships ( see Lissajous figures ) that likely point to a dCO2 SST relationship rather than direct CO2 SST linkage.

    Does not surprise me that there is such a mix in view of variety of in-flux , out-flux conditions that exist.

  33. Greg Goodman says:

    when studying time series , don’t be too keen to throw out the time content of the data. In this case it means drawing a line graph , not isolated dots.

  34. Greg Goodman says:

    Scan my comments and graphs in this thread to see discussion and examples of the significance of phase and joining the dots:

    http://euanmearns.com/uk-temperatures-since-1956-physical-models-and-interpretation-of-temperature-change/#comment-294

  35. William Astley says:

    A quick visual scan of the changes of CO2 by year indicates there is a problem with the standard theory (Bern model) and basis of IPCC report Vs observations. http://www.esrl.noaa.gov/gmd/webdata/ccgg/trends/co2_data_mlo_anngr.pdf

    Our thoughts concerning the observations are affected by the standard paradigm that has been repeated ad infinitum. To determine what is cause and what is effect the standard analysis technique is lead/lag analysis. It is interesting that we have spent two trillion dollars on green scams prior to doing lead/lag analysis to determine the cause of the CO2 increase in the atmosphere.

    The phase relation between atmospheric carbon dioxide and global temperature by Humlum et al, August, 2012.

    http://scholar.google.ca/scholar_url?hl=en&q=http://xa.yimg.com/kq/groups/18208928/233408642/name/phase%2Brelation%2Bbetween%2Batmospheric%2Bcarbon%2Band%2Bglobal%2Btemperature.pdf&sa=X&scisig=AAGBfm2_FClsSVBbTLdzlwJJytToRLHpNw&oi=scholarr&ei=N-SVUvKOD9PtoATG6IHgCQ&sqi=2&ved=0CCsQgAMoADAA

    “From this, changes in atmospheric CO2 appear to be initiated near or a short distance south of the Equator, and from there spread towards the two poles within a year or so. En route, the signal presumable is modulated by local and regional effects, as is indicated by the much larger annual CO2 variation (not shown here) in the High Arctic, compared to that recorded at the South Pole. There is however no indications of the main signal originating at mid-latitudes in the Northern Hemisphere as would be expected from the release pattern shown in Fig. 12.”

    “Summing up, our analysis suggests that changes in atmospheric CO2 appear to occur largely independently of changes in anthropogene emissions. A similar conclusion was reached by Bacastow (1976), suggesting a coupling between atmospheric CO2 and the Southern Oscillation. However, by this we have not demonstrated that CO2 released by burning fossil fuels is without influence on the amount of atmospheric CO2, but merely that the effect is small compared to the effect of other processes. Our previous analyses suggest that such other more important effects are related to temperature, and with ocean surface temperature near or south of the Equator pointing itself out as being of special importance for changes in the global amount of atmospheric CO2.”

  36. MikeP says:

    If you cannot control for other effects than CO2 directly, then you have nothing. For example, some comments above have pointed out biological effects such as photosynthesis and shell formation. But CO2 is not the only driver of these. Upwelling brings both cooler water temperatures and nutrients. These are the most biologically active regions around. The warmer gyre centers such as the sargasso sea have warmer waters and are largely deserts. It would be useful to know where the exact ship tracks and data collection points were.

  37. Gamecock says:

    Little atmospheric gas will enter into the ocean without wind or waves.

  38. dccowboy says:

    Unfrozen Caveman said:

    “We escaped the fate of Venus in large part due to the formation of calcium carbonate by marine organisms, that pulled nearly all of the original CO2 out of the atmosphere to create limestone”.

    we escaped the fate of Venus because of several factors, some of which are, earth has a magnetic field whereas Venus does not, Venus is much closer to the sun and therefore receives a LOT more solar radiation than earth, it appears that life never got started on Venus and we are finding out that early life forms contributed a great deal to the modification of earth’s atmosphere, Venus has no Moon.

    I weary of the comparisons of earth and Venus simply because they are of similar planetary mass. The two are entirely different.

  39. Old England says:

    Willis,
    What depth were they measuring CO2 at? I assume there will be a layer at the surface where CO2 exchange with atmosphere occurs – higher water temperatures will mean more out gassing from the ocean from greater depths and thus higher CO2 concentration at the exchange layer ? Lower temperatures and the opposite occurs with presumably a lower concentration through less out gassing ? As to the differences between atmospheric and ocean CO2 levels I wonder if they plotted in wind speeds and surface water speeds and directions of each as this could presumably create huge anomalies in concentrations.

  40. wsbriggs says:

    Purely physical chemistry explanations of biospheres could be poor matches to the real world where life reverses entropy locally. It would help to know the biological composition of the sea water as well. Simple, this planet isn’t, nor is the rest of the Universe.

  41. DHR says:

    Willis,

    I am not sure the data mean anything.

    The Scripts paper says the “surface” water measurements were taken from a sea chest of unknown location. This class of tug had a draft of 13 feet and sea chests for intake of seawater (primarily for engine cooling) were most always low in the ship to make sure they were underwater as the ship is rolled and pitched – which these ships did a lot of. I don’t know if a depth of a bit less than 13 feet means “surface” for the purpose of your discussion.

    Also, the Scripts paper describes how the air intake was switched depending on the relative wind direction to avoid contamination of the samples by the exhaust of the ship’s diesel engines. Air can swirl about a ship in bizarre ways and sea air is, as you know, burdened with sea mist (with its entrained CO2 I suppose) and salt. On windy days more than less. I found no data that would show whether the intake switching was successful or whether differences between windy and calm days were measured and accounted for. Maybe not.

  42. Bob Greene says:

    Nick Stokes says:
    November 27, 2013 at 4:02 am

    I agree. It looks like they were measuring pCO2air and pCO2water. If they were they were trying to get the flux (difference in partial pressures) that’s the way they would do it. Transport phenomenon would be dependent on temperature and surface layer turnover.
    Henry’s law describes the prime driver http://chemengineering.wikispaces.com/Henry's+law
    These guys have a good summary description of sea water flux http://ocean.mit.edu/~mick/download/Quick-tour-of-carbon-cycle-2011.pdf
    And, as usual, John Daly was there with the firstest and mostest
    http://www.john-daly.com/co2-conc/ahl-co2.htm

  43. Greg Goodman says:

    OK, looking at the data files that Willis linked to, it’s not the CO2 in sea water but the “equilbriator” CO2 concentration. ie the level of atm CO2 with which the water is at equilibrium.

    It can be taken are representing the partial pressure in the sea water and thus the difference used by Willis is that which would drive out-gassing or absoption processes.

  44. lenbilen says:

    Thank you for this survey. It makes sense to me. The CO2 cycle is about 10 years and the oceans contain 60 times more CO2 than the atmosphere. The rain forests and the Gobi desert has the highest concentrations of CO2 on land and parts of Siberia the least.
    Blame it on the clouds. In the north snow and rain absorb CO2 from the air, and it finds its way to the ocean. It is cold so it can absorb a lot which goes into the icy ocean. In mid temperate regions less clouds, less rain. In the tropics the ocean evaporates CO2 even more than the water and the thunderstorms reabsorbs CO2 in the higher elevations which rains down and re-evaporates.
    In the Gobi desert all the cold water coming from the mountains evaporates, raising the CO2 level.

  45. F.A.H. says:

    Looking at the linked paper I note first that the data for CO2 in air across all latitudes was generally quite flat (i.e +- 5 ppmv or so) around 320 ppmv. In contrast, the values for water varied about an order of magnitude more about +-50 ppm. The water measurement techniques (“equilibrator”) varied from cruise to cruise and appeared significantly more correction dependent and systematic error prone than the air measurements. Before doing any interpretation of the data I would go through the experimental details a bit more, particularly the water measurements and corrections.

    Secondly, the atmosphere might be much better mixed than the ocean. Atmospheric wind speeds can average 10 or 20 m/s and upwards (near the surface) and turbulent mixing due to diurnal variations and turbulent boundary layer flow should exceed that of similar phenomena in the ocean (based on Reynolds number arguments). Ocean currents seem to run 1 m/s or less and the mixed layer ( from a few to a few 10s of meters) seems to depend on the relative calmness of the sea surface and varies greatly with atmospheric temperature (i.e weather) and the seasons as well as parts of the ocean. It looks to me that there is a lot more opportunity for variation in the water measurements. I would have liked to see them simultaneously measuring salinity or some other chemical markers to scope mixing and general homogeneity of measurements. It would have been interesting to see whether salinity or some other constituent (nitrogen or whatever) varied in concert with CO2. Salinity in the upper ocean layer seems to vary between about 30-40 parts per thousand over the oceans (on a large scale). http://www.shorstmeyer.com/msj/geo130/salinitypatterns.pdf

    Anyway, I am no expert in any of these things but I would spend a bit more time understanding the measurement details before expending a lot of energy trying to interpret the plot above.

  46. Greg Goodman says:

    Nick Stokes: “All sea water loses CO2 toward summer, and takes it back before winter.”

    Not necessarily. It may out-gas quicker in summer and slower in winter, or absorb slowly in summer and quicker in winter.

    Then you may need to comment on the tropics which don’t have winter and summer.

    However, time of year will be relevant factor.

  47. MattE says:

    I’m curious if the cold water/CO2 effect is confounded by WHERE the cold water/CO2 measurements were taken. For example, the 5C water air/water CO2 temps are more likely taken near Anchorage Alaska or Greenland and the 25C+ measures are tropical. Your curve fit implies ‘all other things equal.’ I submit that that is almost certainly not the case. Imagination can run wild with many reasons why, differences in ocean fauna, CO2 sinks, etc, air/water mixing differences, seasonal changes… It would be one thing if all these temps were from one place, so that would be controled for, but they are clearly not.

  48. phlogiston says:

    According to the NASA earth fact-sheet,
    http://nssdc.gsfc.nasa.gov/planetary/factsheet/earthfact.html

    the masses of ocean and atmosphere are:
    atmosphere: 5.1 E18 kg
    ocean: 1.4 E21 kg

    With atmospheric CO2 at 400 ppm, the mass of CO2 in the atmosphere is 2 E15 kg

    Therefore, if ALL the CO2 in the atmosphere were to be instantly sucked into the ocean (and evenly mixed), that would result in an increase in the concentration of CO2 in seawater of about 1.5 ppm.

    How can this represent a threat of acidification of the ocean?

    So it only mixes at the surface? OK, then how does heat from AGW get down to below 2000m depth?

    Can they really be as wrong as this?

  49. Retired Engineer John says:

    Willis, I like your open mind. Remember your Argo float graphs that you posted, I believe it was in early 2012, where you showed how ocean temperature is limited to 31C. There is another piece to this puzzle, the PH of the tropical – subtropical oceans. The warm layer is approximately one PH number lower than the cold ocean. The reason generally given for this difference is the effect of photosynthesis on PH; however, if you check the world wide distribution for photosythesis, you will find that it is most active in the high latitudes. This is because the layering of the tropical ocean in inversion layers limits the flow of nutrients and thus limits the reaction. The amount of photosysthesis in cold regions is much higher. This means that some other reaction is responsible for the change of the PH in the warm ocean.

  50. fhhaynie says:

    Solubility of CO2 in water is not the only factor to consider. In sea water there are two significant processes that affect the amount of dissolved CO2. One is biological (phytoplankton blumes etc.) and the other is inorganic formation of carbonates and bicarbonates (both soluble and insoluble). It appears that below 17 degrees the biological processes dominate while above 17 degrees the inorganic processes are in control. Also,land based biological activity has a strong effect on the atmospheric concentration of CO2 over the oceans. Another thing to consider is that frozen water does not absorb CO2.

  51. Gene Selkov says:

    Geographical, seasonal, and time-of-the-day splits could bring some order into this mess, but even under the assumption of gas solute equilibrium (which I believe is achieved within minutes under all these conditions), there will be a lot of variation that is difficult or impossible to control for.

    If life has any effect on this, the effect will not be simple. There are multiple producers and consumers of CO2, O2, and N2 in ocean water, they interact with each other, and even in isolation, each kind can behave in interesting ways. For example, it can appear and disappear:

    http://www.lmd.ens.fr/geomix/Lectures/Adrian_Martin/Lecture_2/Lecture-2-HTML-Explorer/patchy1_fichiers/slide0024_image016.gif

    Technologically, measurements taken 50 years ago would be the same as now — no better, no worse; probably a bit more expensive than now because data logging is now automatic.

  52. H.R. says:

    I’m wondering; what was the barometric pressure when each reading was made? Should that be another axis? And… how close together were the readings? Did they drive to an area, park and take multiple readings? What is the variance in the same location at roughly the same time? Hmmm… Let’s go look……………………………….. OK… I’m back…

    I only had time to read briefly over on the Scripps site, but when I see something like this quote;

    “The atmospheric air stream on the LUSIAD cruise displayed a diurnal cycle in measured CO2 mixing ratio [Waterman et al, 1996, p. 20-21], likely caused by degassing of the plastic airline when exposed to sunlight. Only nighttime air data was considered free of this effect and thus acceptable.”

    then, I wonder if all the data on Willis’ plot is all apples or if there might be more than a few oranges, lemons, and cacti mixed in on the plot? What data was thrown out from the other cruises?

    Thanks Willis. This is interesting. I’m going to have a longer look-a-see on the Scripps site over the holiday weekend.

  53. michael hart says:

    F.A.H. says:
    November 27, 2013 at 6:12 am
    ” It looks to me that there is a lot more opportunity for variation in the water measurements. I would have liked to see them simultaneously measuring salinity or some other chemical markers….”

    Me too.

    I have read other sources saying, quite reasonably in my view, that oceanic pH measurements are almost useless without salinity measurement and adjustments. CO2 measurements are, of course, sensitive to pH.

  54. Crispin in Waterloo but really in Ulaanbaatar says:

    @Willis and Retired Engineer and lenbilen

    There are some interesting hits and a lot of blanks in here today.

    Learn from Bob Tisdale: upwelling ocean currents bring things that went under 800 or 1000 years ago.

    As this a really ‘macro’ look at subject, here are two macro observations:
    1. The warmer oceans with the higher CO2 levels are rainier places than the colder and dryer oceans. Rain carries a great deal of CO2 into the ocean – much more than the ocean can sustain because it a) can only retain a certain level of solvated molecular CO2 whereas fresh water is much better at this ‘skill’ and b) there are so many CO2-eating activities going on in sea water (making carbonic acid out of only some 1% of it – don’t believe the guff).

    lenbilen: >The rain forests and the Gobi desert has the highest concentrations of CO2 on land and parts of Siberia the least.

    Parked as I am on the north edge of the Gobi I will toss in that water droplet clouds blowing in from any direction evaporate in the air over the Gobi most of the time releasing much more CO2 than lakes and streams which are buffered (a lot) by rocks and sand.

    2. The upwelling of CO2-rich cold water that is heated as it arrives at the surface is a very strong emitter so one would expect it to be higher than the air above it. The chart of course does not have upwelling/downwelling attached to each dot.

    So can generalize about the rainfall stripping the atmosphere in the wet tropics (as per global CO2 charts) and maintaining it in the warm oceans, even without upwelling. After entry, the salt water environment tries to expel some of it

    The combination of being up/downwelling and the rainy /dry areas provide the large amount of scatter. In a still sunny ocean, Henry’s law governs the sea water concentration. But it also governs the concentration in fresh water droplets (rain). As soon as it rains, the sea water is ‘overloaded’. That explains why the top can be warm and higher. I presume everyone has noted that the level of CO2 in sea water is quite different from CO2 in fresh water.

    Have some fun:
    http://www.thuisexperimenteren.nl/science/carbonaatkinetiek/Carbondioxide%20in%20water%20equilibrium.doc

    20 deg water holds a lot less CO2 that 5 deg water: “At 20 C the CO2 content of [fresh] water is 0.029 mol/litre (1.28 g/litre)” (ibid) but 3 g at 5 C. That is a very big difference.

    The only way to get an increase is to have brought it from below (old), or poured in from above where it disperses either down or up and out (new).

  55. Chris Riley says:

    Is it now time to demote “Henry’s law” to “Henry’s suggestion” ?

  56. RichardLH says:

    Willis: Did you honour the data quality flag which the paper mentions as there was apparently significant diurnal contamination noted along with other data quality issues?

  57. Jim G says:

    “Say what? I gotta confess, I have little in the way of explanations or comprehension of the reason for that pattern … all suggestions welcome.”

    A meaningless scatter diagram from which one should draw no conclusions even were it some type of controlled, structured or random sample, which it is not. Beating such data with a statistical hammer is a waste of time.

  58. Gene Selkov says:

    michael hart says:

    CO2 measurements are, of course, sensitive to pH.

    Not measurements themselves — not in a wide enough range of pH around neutral — but ions in water can affect gas solubility.

    Typical pCO2 measurements *are* pH, measured behind a gas-permeable membrane in contact with the target medium and calibrated in partial pressure units using ambient air, calibration gas, or some calibration solution magic that provides a buffered source of dissolved CO2.

  59. R. Craigen says:

    My first thought is that PPMV is a poor measure because of its different meanings in non-homogeneous fluids versus roughly homogeneous (but chemically heterogeneous) gases. My second thought is that there’s something seriously wrong with this data, or there’s an elephant in the room. Assuming that the only relevant correlative variable is temperature, the variance and the poor correlation coefficient here suggests that the data is very dirty and you can’t really see the relationship. Whatever relationship there is here is overwhelmed by some other factor(s). Salinity, maybe, I’m guessing? Temperatures taken at day versus night (consider effects of penetration of sunlight into shallow water regions)? How about more obvious things such as wind patterns and water turbulence due to storm, tide or current activity — both of which affect mixing of “deep” and “shallow” layers of both substrates, which may significantly affect the data?

    Also, I wonder what “sea surface temperature” is, and whether it is an appropriate variable here? Is it a water temperature, or an atmospheric one? How is it taken? Does humidity play a role? What would happen if you took both water and air temperatures and plotten their difference against the CO2 difference?

    To many “wait a minute, what if”s here for me to believe this data is saying anything significant.

  60. Doug Proctor says:

    There are multiple patterns in this. It is inappropriate to put one trend in (though that is what you first do). I’ll bet that there are separate patterns based on position/basin/region and time.

    This information is important for two questions/observations I made recently (to me): that the seasonal variation in CO2 content as measured at Mauna Loa is uni-modal in a world that is bi-modal (by temperature and time of maximum organic activity FOR two hemispheres).

    Intuitively I would expected two peaks and troughs reflecting increased/decreased absorption of CO2 in sea water during cold/warm periods, and increased/decreased production/absorption of CO2 by plant matter in the growing, stability and decomposition phases. I would not have expected a nice balancing of these factors, as the hemispheres are not equal for either temperature changes, percentage of oceanic waters (of the same temperature variations) or plant growth. I would expect such a simplicity if there was one overwhelming factor that determined CO2 variation.

    The overwhelming factor I see is a REGIONAL surface sea water temperature. The times of peak CO2 is beginning May, the low, mid-October. That is a 4 1/2 month split – in a 12 month year. But sea surface temperature can also create plankton blooms and die-offs, so, as shown by Mauna Loa “adjustments” and cleaning, the asymmetric, unimodal style looks to me to reflect a region of seas that
    1) come to peak warming in May and peak cooling in October – releasing CO2 in May and absorbing it in October, OR
    2) come to a low biogenic activity in May and peak activity in October – allowing decomposition to dominate in May, releasing CO2, and pulling it out of the atmosphere in October when photosynthesis is at its height.

    Both scenarios would involve, obviously, a planetary level smoothing of all factors. However, the dominance theory says we search for the ocean area that “counts” – which is probably the Indian/West-Central Pacific. The rest of the planet is noise; only that region provides the signal.

  61. Dave in Canmore says:

    I found this paper to be a good read on the subject
    http://www.ldeo.columbia.edu/~csweeney/papers/taka2002.pdf

    from the Abstract:
    A zone between 40 and 60 latitudes in both the northern and southern hemispheres is found to be a major sink for atmospheric CO2. In these areas, poleward-flowing warm waters meet and mix with the cold subpolar waters rich in nutrients. The pCO2 in the surface water is decreased by the cooling effect on warm waters and by the biological drawdown of pCO2 in subpolar waters. High windspeeds over these low pCO2 waters increase the CO2 uptake rate by the ocean waters.

  62. Hoser says:

    Air-water gas exchange is not efficient without mixing. In the ocean wave action is needed. Under what temperature conditions would there be more wave action? These ranges might be when the air/water partial pressures are more comparable.

  63. michael hart says:

    Gene Selkov says:
    November 27, 2013 at 8:04 am
    michael hart says:

    CO2 measurements are, of course, sensitive to pH.

    Not measurements themselves — not in a wide enough range of pH around neutral — but ions in water can affect gas solubility.

    Typical pCO2 measurements *are* pH, measured behind a gas-permeable membrane in contact with the target medium and calibrated in partial pressure units using ambient air, calibration gas, or some calibration solution magic that provides a buffered source of dissolved CO2.

    Let me be more explicit. The amount of free CO2 is affected by CO2/bicarbonate/carbonate equilibration [and the rate, since this is not at equilibrium], which is dependent on pH.

  64. rgbatduke says:

    Willis, the figure bothers/puzzles me too. The red line is meaningless, for one thing. For another, there is clearly evident structure, multiple bands at a statistically significant level, across the entire figure but especially in the range from 17 C to 25 C. Warmer than 25 C there may be structure as well, but the bands appear to have merged and smeared.

    I suspect that part of the structure reflects the effects of ocean currents. Ocean currents can take warm water with an overpressure of CO_2 and transport it to colder waters where it mixes but takes time to re-equilibrate. Sampling within currents (e.g. the Gulf Stream) would then show banded structure like that seen.

    The other thing that I suspect is sampling error. You say they drove around on four cruises, sampling along the way. In the temperate 17-25C range, there appear to be four bars. A coincidence? I doubt it. The ocean’s surface CO_2 content is evidently inhomogeneous (that much is correct beyond any doubt) but it also has a strong spatial autocorrelation, again probably due to surface transport and upwelling. Note also the tremendous sparseness of the data at colder temperatures compared to the data at warmer temperatures. In part this reflects (no doubt) the Jacobean and shape of the continents and oceans — there is a lot more water at tropical latitudes than there is at the poles — but I’d bet my sweet bippy that it also reflects the selection bias of researchers to prefer ocean cruises in the warm, sunny tropics with lots of interesting places to stop and things to see relative to cruising around the Cape of Good Hope or Tierra del Fuego or knocking around Iceland or the Bering Straits — presuming one can get in through the ice and so on. There are hardly any samples from 4C water, and none from water at the saltwater freezing point. Nobody from California wants to spend their time wearing mittens and trying not to touch metal because it will freeze your skin by sticking to it.

    With sparse, biased samples, it is difficult to draw any conclusions from this data.

    I’m surprised that they didn’t put CO_2 sampling into the ARGO floats. What the hell were they thinking? You’re going to spend a small fortune per float anyway, and the marginal cost of additional testing hardware is tiny compared to the cost of funding junkets for researchers to badly sample a biased trajectory through the ocean.

    If I were going to sample the ocean, I would take the globe and crank out random coordinates on its surface (intelligently, not treating lat/long as scaled uniform deviates). Then I would use a computer to solve the problem of efficiently visiting the sites, and either arrange cruises to systematically work through the list (ideally starting from multiple locations, not just California) or devise e.g. a computer/radio controlled, unmanned solar powered “ship” that would work its way through the list without human intervention. Or I’d go and stick CO_2 sensors on board ARGO floats the next time they are serviced and learn about the spatiotemporal CO_2 profile of the entire ocean to depth.

    The really interesting, tantalizing question that the data above is insufficient to answer is — in the warmest waters there is a really substantial, quite possibly robust, CO_2 overpressure in the water relative to the air. One has to wonder — is this CO_2 moving INTO the air (predominantly) or OUT of the air? The usual assertion is that cold water holds more CO_2, but this graph suggests otherwise in the only place that really matters, at the surface. The other thing that bothers me is that the graph doesn’t present the actual atmospheric CO_2 associated with each dot, so we cannot answer some enormously interesting questions, such as what the mean atmospheric concentration of CO_2 in ppm at sea level actually was, averaging over all four cruises. Did the data reveal that CO_2 is indeed “well-mixed” so that the averages more or less match those observed at Mauna Loa? Or did they get some other answer? At places where oceanic CO_2 was higher than atmospheric CO_2, was atmospheric CO_2 higher than the Mauna Loa mean or lower? Is there evidence, in other words, that the CO_2 is moving in or moving out in the warmest waters!

    Maybe all of this is revealed in other data taken during the voyages, but now you’re gonna have to winkle it out too — the figure above isn’t enough to draw any conclusion beyond “four voyages were made and one can easily guess the spatiotemporal pattern of the sampling from the appearance of irrelevant banding in the data”. And the fact that four samples — not the hundreds that the graph APPEARS to show but FOUR for FOUR trajectories — is not a lot to draw conclusions from with the smear and structure already apparent in the four trajectories.

    rgb

  65. Walter Allensworth says:

    How does time of day of the sample change this graph?

    We know that CO2 levels above corn fields vary dramatically during the day, bottoming out around noon-time. Plants suck half the CO2 out of the air in roughly the first 6 hours of the day.
    Photosynthetic organisms in the water could do the same thing to a greater or lesser degree.

    see: http://jonova.s3.amazonaws.com/graphs/co2-absorption/chapman-corn-field-fig-1-co2.gif

  66. Canman says:

    Unfrozen Caveman, Dodgy Geezer and dccowboy on escaping the fate of Venus,

    The Sun is understood to have increased in brightness over geological time. This might be pertinent.

  67. Jquip says:

    @Willis: “Say what? I gotta confess, I have little in the way of explanations or comprehension of the reason for that pattern … all suggestions welcome.”

    Easy, ceteris paribus is only valid when the ceteris is paribus. The lab and life are not always the same, or even in the same area code: Unless you start accounting for the confounds.

    All the mentions of confounds so far seem reasonable to some degree or another. But I’d wager the majority effect here is one of aerobic life getting its groove on. Not as catchy or as sane to put forward and a cap and trade idea on carbon based life though…

  68. Werner Brozek says:

    Would you have a similar graph with respect to oxygen? I am wondering if there are more animals in the tropical regions that breathe more oxygen and emit more CO2.

  69. Gene Selkov says:

    michael hart says:

    Let me be more explicit. The amount of free CO2 is affected by CO2/bicarbonate/carbonate equilibration [and the rate, since this is not at equilibrium], which is dependent on pH.

    True, that, although this dependence is bi-directional. Incidentally, this is just the system that is used in the most common type of pCO2 probe. It has a carbonate/bicarbonate buffer inside that is monitored with a regular pH probe.

    To make things more interesting, marine photosynthetics have carbonic anhydrase, which allows them to uptake bicarbonate. They don’t care what form of inorganic carbon is there, so there is more than one way they can shift equilibrium. They respire, too.

  70. michael hart says:

    Gene Selkov says:
    November 27, 2013 at 9:04 am
    To make things more interesting, marine photosynthetics have carbonic anhydrase, which allows them to uptake bicarbonate. They don’t care what form of inorganic carbon is there, so there is more than one way they can shift equilibrium. They respire, too.

    I’m delighted to hear you say that, Gene. I occasionally point out the same thing, but it gets roundly ignored. In fact all life forms make extensive use of carbonic anhydrase, not just photosynthetic organisms. How long the activity persists in dead vegetative matter is another interesting question.

  71. sergeiMK says:

    Plants (phytoplancton etc) respire in dark – give out CO2 and photosynthesise in light- take in CO2
    The biggest variation in yearly CO2 is at northern most monitoring stations. The CO2 variation is therefore likely to originate around these.

    Decomposition requires warm temperatures for the bacteria to work.At the end of summer temperatures are falling rapidly so decomposition will not release CO2 rapidly and certainly would not continue into December. This suggests that spring growth and autumn decomposition would not cause the CO2 dip.
    CO2 creating carbonic acid in the sea would not release O2 nor absorb O2

    this plot shows that the change in O2 is the inverse of the change in CO2 – Just what you would get with 24 hour daylight vs 24 hour dark. The yearly variation is simply the plants breathing!!

    You will note that there is a general decline in O2 over the years. Burning plant growth are suitable causes dissolved CO2 emerging from warmed oceans is not the cause.

    http://bit.ly/Ipcj4R

  72. sergeiMK says:

    CO2(aq) + H2O H+ + HCO3-
    i.e. there is no absorbed O2 nor released O2 as sea water takes up/releases CO2

  73. Robert Gyurik says:

    Henry’s Law is valid for standard conditions, meaning pressure is a variable that also has to be normalized (controlled) to make sense of the equation. At higher pressure, more CO2 dissolves in surface water. The Scripps Oceanographic vessels gather data about atmospheric pressure also, along with the ones mentioned here. It would be simple to normalize the data, making pressure a constant. One must isolate all of the ancillary variables if the relationships among the key study variables are to be understood properly.

  74. cd says:

    Robert

    It’s hard to see what is going on unless the raw data for both data series is provided. But as you say the role of both temperature and pressure cannot be properly resolved without “normalising” the pressure.

    The other thing that makes this a difficult issue is that one would also need to assess the amount of physical mixing and the composition of the water with respect to the “bicarbonate system”. Furthermore, I suspect the mere presence of biological activity would have a role to play.

  75. CRS, DrPH says:

    Canman says:
    November 27, 2013 at 8:41 am
    Unfrozen Caveman, Dodgy Geezer and dccowboy on escaping the fate of Venus,

    The Sun is understood to have increased in brightness over geological time. This might be pertinent.

    Thank you, I’m certain it is.

    Although Earth and Venus have certain physical similarities, they are quite distinct and were destined to evolve into two distinct planetary environments:

    a) Venus is a very dry planet, and the Venus we see now is nothing like what once existed. The reasons for the loss of its water are still in dispute, please see:
    http://www.vanderbilt.edu/AnS/physics/astrocourses/AST101/readings/water_on_venus.html

    b) Besides carbon dioxide, Venus’ atmosphere contains vast amounts of sulfuric acid, which actually [accounts] for the lovely clouds we see in photographs. The combined molecular weight of the atmosphere on Venus is far greater than Earth, which is one reason for the hellish conditions on the surface (higher pressure at the surface, temperature etc.).

    c) It seems obvious to say this, but Venus is much closer to the sun, and the inverse-square law dictates that Earth receives proportionally much less energy from the sun by the square of the distance.

    Comparisons of Earth to Venus by jokers like Hansen drive me nuts! This one is characteristically bad: http://www.climatevictory.org/venus.html

  76. John West says:

    ”when the water is cool, it contains less CO2 than the overlying air … but when the water is warm, it has more CO2 than the overlying air.”

    That’s because the pCO2 of the overlying air is nearly irrelevant to the pCO2 of the seawater when compared to temperature, salinity, and biological activity.

    ”The pH and the pCO2 are not simply functions of the amount of CO2 in the overlying air.”

    http://wattsupwiththat.com/2011/10/25/the-reef-abides/

  77. Willis Eschenbach says:

    Nick Stokes says:
    November 27, 2013 at 4:02 am

    Willis,
    I don’t think the water measurement reflects concentration of CO2, and I’m sure it isn’t ppmv of water. It’s described in your link as pCO2, which would be the partial pressure of CO2 in equilibrium with the seawater.

    In that case, there’s no particular expectation about variation with temperature. With no flux, it would be zero at any temperature. What it does reflect is which way CO2 is moving.

    On that basis it should indeed be higher in warm water, because that is thought to be a region of degassing. So pCO2 must be higher below the surface. CO2 moves down a gradient of pCO2.

    In fact, though, it would be very seasonally dependent. All sea water loses CO2 toward summer, and takes it back before winter. So timing of the readings would be important.

    Thanks, Nick. My question is, why is it so high, up to 100 ppmv higher than the concentration in the overlying air?

    w.

  78. Willis Eschenbach says:

    Old England says:
    November 27, 2013 at 5:32 am

    Willis,
    What depth were they measuring CO2 at?

    This and many questions are answered in the cited reference … in any case, it’s from the surface.

    w.

  79. jorgekafkazar says:

    My expectation, prior to seeing the plot, was that there would be a huge blob with no particular correlation (r² ~ 0.1). Well the blob is there on the right side, a shotgun blast. The data on the left side is sparse and probably has no relevance compared to its uncertainty. The interesting detail in the center is probably an artifact of the methodology, plus wind and currents. Drawing a curve or curves through this stuff is like drawing canals on Mars, and just as useful.

    Good comments, rgb, Nick, John West and many others, including lemiere, who kicked off the comments. Wind permits the equilibrium to have been established where the sample was not taken. Also, the fact that one variable (CO² in air) didn’t vary (much) could mean that the ordinate variable was poorly selected and the study is irrelevant. I’m wondering if the error bars are wider than the distance from the center of the Blob to the y = 0 axis.

  80. steve says:

    Seems like there is a lot of embedded structure, which implies something else is causing the correlation. You might try making the same plot for different air temperature bands to see if it simplifies.

  81. Aphan says:

    Not sure if posters are being silly, or trying to come up with arguments that are supposed to make the data make sense in an AGW argument, but Macha and others have said things along the lines of:

    “Warmer water can absorb and hold more CO2, than cold.” Or that “warm water holds more CO2 than cold water”.

    Not true. It’s the opposite. Cold water absorbs and holds more dissolved gas than warm water does.

    That’s why the ocean is a perfect CO2 sink. The AGWarmists argument is that because the ocean is warming, it will not be able to continue to absorb the CO2 humans are spewing into the atmosphere as well-because of the principle that warmer water outgasses C02..it does not absorb more.

    BUT saltier water does not absorb as much as fresh water. And saltier water is denser, so it would sink below fresher water. Add in ocean currents, time it takes for C02 the gas to dissolve in water, upwellings, winds, pressures etc and I’d expect there to be a difference between the two systems.

    http://blogs.ei.columbia.edu/2010/07/07/does-temperature-control-atmospheric-carbon-dioxide-concentrations/

  82. Some might find this paper interesting and there are many more out there in the free world. It is very interesting that the results of the research seems to tilt toward the FUNDING SOURCE – Follow the money is now not just a political reality it has infected Science.

    http://www.usc.edu/dept/chemistry/loker/ReversingGlobalWarming.pdf

  83. albertalad says:

    I would be interested in knowing whether they took samples from calm water or rough water or heavy seas – which in part may well explain why CO2 was high or low depending on the actions of the ocean itself.

  84. Willis Eschenbach says:

    I’ve added an update to the head post as follows:

    [UPDATE] By popular request, here is the same data, but in absolute rather than relative units and without the lowess curve.

    Figure 2. As in Figure 1, but showing the CO2 content of the surface seawater directly. Atmospheric CO2 varied very little during the time of the measurements.

    My main question in all of this is, how does the CO2 content of the seawater get to be up to 100 ppmv above the CO2 content of the overlying air? It seems to me that the driver must be biology … but I was born yesterday.

    Regards,

    w.

  85. Gary Pearse says:

    johnmarshall says:
    November 27, 2013 at 3:02 am

    “Dissolved CO2 remaining in the water is used bu planktonic and other plants to photosynthesize. These chemical reactions speed up with temperature rise.”

    Also, things are complex in terms of the relative aqueous concentrations (K=equilibrium constant at a given temperature) of the linked species: H2CO3, CO2, (HCO3^-, H^+) (the “first” dissociation of H2CO3) and (H^+ CO3^-2) the second dissociation. [H2CO3]/[CO2] = K1; [H+] * [HCO3]/[H2CO3]= K2 and [H+]*[CO3^2-]/[HCO3] = K3.

    Going from 0 to 30C, K1 is ~ halved; K2 is ~ doubled and K3 is ~ tripled. In all this, the activities described by johnmarshall are happening as well as the inorganic carbonate precipitation with Ca2+ and Mg2+ in the seawater.

    Making full sense , on the face of it, of this remarkable unexpected relationship between CO2 in seawater with temps would require experimentation with and without Ca-Mg and plankton. Since CO2 is the crux of all the CAGW issues, these are experiments that should be done. It seems that all- important CO2 behavior is, like other people-heat effects, a hand waving exercise by the climate and sistren. Please don’t let Al and the Science Guy do the experiments!

  86. Gary Pearse says:

    Oops, I lost the brethren!

  87. Ulric Lyons says:

    I should imagine the plot would be very different for La Nina years:
    http://www.pmel.noaa.gov/pubs/outstand/feel1868/text.shtml
    http://www.pmel.noaa.gov/co2/elnino.html

  88. Edim says:

    In the atmosphere there’s background concentration, which is more or less global. This may be different in the sea (surface).

  89. Aphan says:

    I haven’t read all the newest posts, so forgive me if I’m saying something that was already said.

    I think it’s the way that the graph has set up the data that is screwing with you Willis. (it does me too) Not the data itself. It doesn’t measure the actual C02 in the water OR the air, it measures the DIFFERENCE between the two and then charts them relative to ONLY on the temperature of the surface water the sample was taken from. The chart is also not a linear chart of the same water over time comparing it’s Co2 rise and fall to the temperature changes of that water, The ABSTRACT says:

    “Carbon dioxide (C02) in the surface water and atmosphere of the Pacitic, Indian, and Atlantic
    Oceans was measured by nondispersive infiared gas analyzer on three oceanographic expeditions from October 1957 and August 1963.”

    They are measuring samples from 4 DIFFERENT oceans on 3 different expeditions, comparing the C02 in the samples to the C02 in the air at the time that sample was taken.

    To clarify (more for myself than anything)

    Let’s say that for all the samples, the atmospheric co2 was roughly the same for a well mixed atmospheric 330 ppm. The left axis shows that we have to subtract that level of Co2-330 from the Co2 measurement in each SS sample and record the difference.

    We take a sample in SS water that is 5 degrees C, and let’s say that the Co2 IN THE WATER is 380 ppm-higher than the CO2 in the atmosphere by 50 ppm. We are constrained to subtract the atmospheric Co2 FROM the ocean Co2 so, 380-330 is a +50 on the chart.

    Now we sample SS water that is 5 C somewhere else. We get a CO2 reading in that water of 320ppm. Same temperatures, but different CO2 levels. We have to subtract the SAME atmospheric Co2 from the Ocean Co2-320-330 is -10 on the chart.

    Then we sample SS water that is 20C. It’s Co2 reading is 180. 180-330=-150
    Another location of SS water is 20C, but it’s Co2 reading is 375. 375-330=+45

    Obviously the CO2 in the oceans surface is NOT as well mixed as the CO2 in the air, and thus the concentrations of it vary widely across the planet, even in places where the ocean surfaces are the same temperature.

    We’re used to viewing such charts as linear in time and looking at the differences between one date and another. This chart just isn’t set up that way and it messes with my head at least. If I’m up in the night, I apologize for suggesting that my inability to grasp the chart is shared by anyone else here.

  90. Lester Via says:

    Looking at the description of the data, it appears to me they are not measuring the CO2 levels of sea water directly, but the CO2 level of an air stream that has been equilibrated with the sea water. If you take an air stream and spray seawater into it and monitor its CO2 content, you would expect the CO2 level in the air stream to increase whenever the seawater is warmer than the annual average SST and decrease when below the annual average SST. All it seems to mean is that the surface waters seldom in equilibrium with the air except when the sea water is close to the annual mean temperature.

    I suspect that if the data were presented in terms of a deviation from the annual average SST
    at the point the sample was collected, much of the apparent randomness of the plot will disappear.

  91. B.Quartero says:

    Indeed, biology! Coral reefs and algae are net contributors of CO2. They “eat” more organics than they store in building their CaCO3 framework. Although full cycle they present a CO2 sink, due to semi-permanent storage of CO2 as limestone, locally, in their prime habitat between 25-30C waters, they appear to contribute to the CO2 production.

  92. Willis Eschenbach says:

    rgbatduke says:
    November 27, 2013 at 8:36 am

    … The other thing that I suspect is sampling error. You say they drove around on four cruises, sampling along the way. In the temperate 17-25C range, there appear to be four bars. A coincidence? I doubt it. The ocean’s surface CO_2 content is evidently inhomogeneous (that much is correct beyond any doubt) but it also has a strong spatial autocorrelation, again probably due to surface transport and upwelling.

    Thanks as always for your interesting comments. Here is the data, divided by cruise:

    Regards,

    w.

  93. David L. Hagen says:

    Willis
    Interesting. The low CO2 appears similar to the downwelling regions of the temperate deserts about 25 – 35 latitude No and So.
    Suggest comparing against surface solar insolation and Hadley cells upwelling/downwelling.

  94. Aphan says:

    Here’s an animation that shows how much atmospheric CO2 levels VARY depending on latitude yearly and over time. https://www.youtube.com/watch?v=k7jvP7BqVi4&feature=player_embedded

    Being that water responds more slowly than air does, it’s easy to see how at certain points in a year, in certain latitudes, the air CO2 would be at a low for the year while the ocean CO2 could be at a high and they could criss-cross each other.

  95. Steve Garcia says:

    1. From the wide variation at any given temperature, I’d say that there are other things going on. There is NOT one factor contributing. Like you said, Willis, you expected the delta to be about 5ppm. And here it shows deltas at any given temp to be ranges up to and over 150ppm – 30 times what you suspected (which did not sound unreasonable).

    2. From the colored cruise graph, three of the cruises look like they will have essentially the same curve as the overall. Only the blue 1957 cruise seems to vary much from the overall.

    So, I think the data is inadequate to come up with an adequate “final” answer. I think it is even inadequate to come up with a really good next level question.

    For complicated problems, the first returns don’t give final answers – they only lead to the next level questions. First level questions are going to be blind groping to a goodly extent. At each level, with better questions (leading to better experiments) come better answers. In my experience that means the first level question is uninformed and mostly ignorant – mostly ignorant of what other factors are involved. As those other factors are brought in, the results begin to make more sense – leading to second level questions that are better and give better results.

    It is premature to think that that one graph is going to lead to a good answer. At best it can lead to pointing in the right direction for the next level of observations/experiments.

  96. Fritz says:

    There is a whole lot of misinformation going on in the comments here; sorry.

    The way CO2 is being measured here (equilibration with air) measures the partial pressure in the water, and in effect, the forcing function for CO2 to enter or leave the water to the atmosphere. Assuming the air temperature in the equilibrator and the water temperature are the same, the temperature, the salinity etc, do not effect the pCO2 at all. The 13 ft draft of the ship might have some effect, but not much, since the ocean surface is usually pretty well mixed to that depth.

    There are only three ways for the surface water to be out of equilibrium with the atmosphere, photosynthesis, which uses CO2 and reduces pCO2, respiration of some sort which raises it, and advection of deep water (commonly high in CO2 due to respiration) into the surface. The total amount of CO2 dissolved in the water in equilibrium with the air depends on the temp, salinity, and most importantly, alkalinity, which in the open ocean, is closely correlated to salinity.

    Here’s my view of your data. In cold water, photosynthesis and respiration are slow (especially in the open ocean where plankton concentrations are relatively low), while mixing due to weather is not, so its not surprising that those sample are generally close to equilibrium. At moderate temperatures, photosynthesis usually exceeds respiration (otherwise the oceans run out of food), and pCO2 should commonly be below the atmosphere. At temperatures above 25 C photosynthesis is inhibited in most phytoplankton, and respiration (mostly bacterial) dominates, using up all the loose organic carbon, and converting it to CO2, and raising pCO2 above atmospheric.

    I suspect the obvious data clusters and “lines” are related to large scale oceanographic features of the water the cruise tracks covered, and a little teasing would pick them out easily enough.

    I’ve actually used an equilibrator like this one in the Chesapeake Bay; we’ve seen pCO2 values as low as 50 ppmv in a dense phytoplankton bloom, and as high as 12,000 or more (it saturated our sensor) in the water filtering out of a salt marsh, and strong diurnal cycles as plankton photosynthesize during the day, and respire at night.

    Here is a link to an Excel spreadsheet that can be used to do lots of calculation on the CO2 system in seawater:

    http://cdiac.ornl.gov/oceans/co2rprt.html

  97. Dr Burns says:

    Willis, it would be interesting to see how, when and where the readings were taken. Different areas of the ocean outgas and absorb CO2 at different times. The data looks very different to the implications of the following plot:
    http://www.rocketscientistsjournal.com/2007/06/_res/Takahashi.jpg

  98. Willis Eschenbach says:

    Fritz says:
    November 27, 2013 at 1:00 pm

    … There are only three ways for the surface water to be out of equilibrium with the atmosphere, photosynthesis, which uses CO2 and reduces pCO2, respiration of some sort which raises it, and advection of deep water (commonly high in CO2 due to respiration) into the surface. The total amount of CO2 dissolved in the water in equilibrium with the air depends on the temp, salinity, and most importantly, alkalinity, which in the open ocean, is closely correlated to salinity.

    Here’s my view of your data. In cold water, photosynthesis and respiration are slow (especially in the open ocean where plankton concentrations are relatively low), while mixing due to weather is not, so its not surprising that those sample are generally close to equilibrium. At moderate temperatures, photosynthesis usually exceeds respiration (otherwise the oceans run out of food), and pCO2 should commonly be below the atmosphere. At temperatures above 25 C photosynthesis is inhibited in most phytoplankton, and respiration (mostly bacterial) dominates, using up all the loose organic carbon, and converting it to CO2, and raising pCO2 above atmospheric.

    Many thanks for that, Fritz, very interesting. I’ll need to consider all of that and run some numbers, but at first look it seems right.

    It also accords with my contention, which is that what goes on in the ocean at all levels is not ruled by chemistry.

    Instead, it is ruled by life, and what life does and doesn’t do.

    Regards,

    w.

  99. Lester Via says:

    Willis, regarding your question “why is it so high, up to 100 ppmv higher than the concentration in the overlying air?” A back of the napkin approximation may help –

    When in equilibrium, the amount of dissolved CO2 in water at 15 deg C is 32% higher* than in water at 25 deg C. Take water at in equilibrium at 15 deg C with atmospheric CO2 equal to 400ppm, put it in a closed container with a small amount of air, heat to 25 deg C., shake hard until equilibrium is achieved and the CO2 content of the air should rise to 528 ppm.

    *Handbook of Physics and Chemistry, 84th edition

    equibrium

  100. Willis Eschenbach says:

    Fritz, a further comment. I don’t find that photosynthesis in phytoplankton is inhibited above 25°C … instead, it seems to be species specific, and there are a number of species who grow fastest at 30°C or above. See the interesting study, Temperature And Phytoplankton Growth in the Sea for further information.

    Here’s a map of chlorophyll concentration, a marker for phytoplankton:

    As you can see, the equatorial Pacific has more phytoplankton than the temperate zones, and there is plenty of chlorophyll in the “Pacific Warm Pool” around PNG and Indonesia.

    Best regards.

    w.

  101. Man Bearpig says:

    “My main question in all of this is, how does the CO2 content of the seawater get to be up to 100 ppmv above the CO2 content of the overlying air? It seems to me that the driver must be biology … but I was born yesterday.”

    Yes, that is an easy one = ‘It’s because of all the fish in the atmosphere breathing out’

  102. kwinterkorn says:

    It seems from the discussion above that the science is not settled—–even the means and method of measurement of something that at first blush seems elemental to any CO2-driven ocean/atmosphere temperature model are not settled. Just as Anthony Watts surface temps studies have shown, we do not even have reliable data to punch into our speculative and minimally scientific models. But apparently some can assert within a degree or two what global temps will be in a hundred years.

  103. Willis,

    The data you plotted are only a fraction of all the data sampled at a few fixed places over the past decades and from a lot of cruises all over the oceans, together with more recent buoys set out over the oceans (still sparce) comparing air pCO2 (~ppmv) with ocean surface pCO2.
    The oldest data BTW were from a German research ship in the 1930’s, measuring pCO2 down to 2000 m depth…

    The near three million measurements were used to compare CO2 in/out fluxes in different area’s of the oceans over the seasons and the net flux over a year. See:
    http://www.pmel.noaa.gov/pubs/outstand/feel2331/images/fig03.jpg
    and
    http://www.pmel.noaa.gov/pubs/outstand/feel2331/images/fig06.jpg

    And the whole story about the measurements and calculations is here:
    http://www.pmel.noaa.gov/pubs/outstand/feel2331/abstract.shtml

    The main reason that there are differences between ocean pCO2 and air pCO2 are:
    – temperature
    – biolife
    – migration speed

    The latter is the main problem: the migration speed of CO2 in water is very low. It is only by wind and waves that CO2 can exchange with the atmosphere at sufficient speed, depending mainly of wind speed. And at the same wind speed about in ratio with the pCO2 difference between air and seawater.

  104. Jaakko Kateenkorva says:

    Thank you Anthony for being the beacon for those navigating in the treacherous waters of politicized science, Willis Eschenbach for this tantalising guest post and everyone contributing to the discussions. I cannot resist the temptation to build on ideas of Phlogiston, UnfrozenCavemanMD, Gary Pearse and others here.

    If the sea mass is thousands times greater than the atmospheric mass, it seems hasty to build a earth encompassing hypothesis around a gas measured in parts per million in air – let along forecast anything based on it. There are other variables to identify and consider. Biosphere is a logical candidate and here is another:

    Sea has an interface with an area we know less about than the surface of the moon. The Seven Sisters cliffs in Sussex hardly are the only natural chalk surface continuously eroded by the sea. They are made of relatively pure calcium carbonate (CaCO3). It is not very soluble in water, but dissolution increases when pH decreases.

    CaCO3 + CO2 + H2O → Ca(HCO3)2

    Because bicarbonate increases water alkalinity, CaCO3 dissolves more in cold than warm water. It precipitates (as limescale) when solutions are heated – releasing CO2 in the process.

  105. Fritz says:

    Those green bands at the equator are driven by equatorial upwelling, cooler (a little), nutrient rich (and I presume CO2 rich) water brought to the surface by the Trade Winds and Ekman transport. Yes, there are plenty of phytoplankton that grow well up to 30 and even 35 C (or we wouldn’t have any in Chesapeake Bay in summer), but generally higher temperatures favor bacterial respiration over photosynthesis.

  106. Steve Keohane says:

    Thanks Willis interesting post. The third graph shows interesting patterns that seem replicated in part by the different cruises, strengthening the reality of their peculiarities.
    The chlorophyll map is very interesting too. Australia’s Outback, N. Africa, the Andes and Rockies have an order of magnitude more chlorophyll than the equatorial and temperate zones. Surprised me that the ocean’s would be that sparse compared too these desert-like areas.

  107. Willis Eschenbach says:
    November 27, 2013 at 1:47 pm

    there is plenty of chlorophyll in the “Pacific Warm Pool” around PNG and Indonesia.

    Most biolife is where there is deep ocean upwelling: these bring a lot of nutritients to the surface, where shortage of minerals is the main constraint. See:
    http://en.wikipedia.org/wiki/Upwelling

  108. Lester Via says:

    Another big problem in determining what all this means is that the term “sea surface” doesn’t seem to has a specific definition as to depth. With regard to CO2, the IPCC report considers the ocean surface to contain nearly twice the mass of CO2 as does the atmosphere while the intermediate depths contain more than fifty times the amount in the atmosphere. Very little of this surface ocean CO2 is transferred to the atmosphere, else the seasonal variations in CO2, as measured at Mauna Loa, would be much larger than is being recorded. These variations are due to the ocean area in the southern hemisphere being much larger that the northern hemisphere while atmospheric mixing is considered to be fairly rapid. This relatively small CO2 variation indicates very little of the available surface ocean CO2 is transferred between the ocean and the atmosphere, in turn, indicating that the ocean surface CO2 doesn’t change much as its temperature changes. When the seawater warms there is a significant surplus compared to equibrium, and conversely there is a significant shortage when it cools. The data Willis plots simply reflects this.

  109. Mike Jonas says:

    Apologies all, but I haven’t read the comments and they probably give the answer many times over: The system is not static, everything is moving. CO2 is emitted mainly by the warm tropics, travels to the high latitudes, and is mainly absorbed there. Then it goes into the deep and eventually goes round again. The atmospheric pCO2 (partial pressure) is lower than the ocean’s where the water is warm, because when water is warmed its pCO2 increases – hence the CO2 emission in the tropics. The CO2-depleted water travels to the high latitudes where it cools, hence its pCO2 decreases, hence it absorbs.

  110. Nick Stokes says:

    There’s an interesting quote at the start of the linked paper. One sometimes hears that AGW is just a scare rustled up by scientists after the ice age scare of the 1970’s failed. In fact, no ice age scare ever came from scientists. Lill and Revelle had it in 1958, IGY Bulletin:

    “…Man, in his burning of fossil fuels and denudation of the land’s surface, may be performing a gigantic geochemical experiment in which the CO2 cycle is being influenced. It is thought we may be increasing the C02 input into the atmosphere by 70% in 40 years, although it is not certain how much of this may be absorbed by the oceans. A substantial increase in C02 content in the air would trap more of the earth’s radiated heat and cause a warming of temperature.”

  111. Lars Tuff says:

    Thanks for this post. Well, obviously someone forgot to take care of the exhaust from their speedboat. This report is bullshit. Someone got a nice trip paid in full with the taxpayer’s money. In that sense, it does not differ from all the other ‘scientific’ pollution from the alarmist camp. It has nothing to do with science, it tells us nothing, it disregards most scientific procedure, it costs a lot, and, as usual, it has nothing to do with reality. But people have been cooking temp. meters for some time, why not have a go at oceanic CO2. As we all know, from climategate, the saying goes: “What can we do to make people believe there is a crisis, when we can find nothing to indicate there is?” Let’s do another nature-trick.

    I have no doubt some peer-reviewed guys will repeat this trip soon, and come up with almost identical results.

  112. William Astley says:

    This also is a good review paper of the history of CO2 atmospheric research and the history of the IPCC shenanigans. The IPCC shenanigans very interesting, as noted the laws of physics change for CO2.

    One of the key points is the resident times of CO2 in the atmosphere. The C14 bomb test analysis (Analysis of the spike of C14 produced by the atomic bomb tests) indicates the resident time for CO2 in the atmosphere is 7 years.) As the surface ocean reservoir is reversible (that is key) the only way C14 can drop to very, very low levels is there must either be mixing of deep ocean water with the surface water and/or C14 must precipitate out. If there is significant mixing of deep ocean water with surface water (this what the heat hiding in the deep ocean hypothesis requires) then the majority of the anthropogenic CO2 will be transferred into the deep ocean carbon reservoir which is more than 50 times greater than the atmospheric CO2 rise. The key logical point is that anthropogenic CO2 emissions are very, very, small compared to the super enormous, deep ocean carbon reservoir.

    The physical implication of the C14 bomb test analysis is the majority of the CO2 increase in the last 70 years was caused by the warming of the oceans rather than the anthropogenic CO2 emissions. Truly fascinating!

    http://folk.uio.no/tomvs/esef/ESEF3VO2.pdf
    Carbon cycle modelling and the residence time of natural and anthropogenic atmospheric CO2: on the construction of the “Greenhouse Effect Global Warming” dogma. By Tom V. Segalstad: Suess (1955) estimated for 1953, based on the carbon-14 “Suess Effect” (dilution of the atmospheric CO2 with CO2 from burning of fossil fuel, void of carbon-14), “that the
    worldwide contamination of the Earth’s atmosphere with artificial CO2 probably amounts
    to less than 1 percent”. Revelle & Suess (1957) calculated on the basis of new carbon-
    14 data that the amount of atmospheric “CO2 derived from industrial fuel combustion”
    would be 1.73% for an atmospheric CO2 lifetime of 7 years, and 1.2% for a CO2 lifetime
    of 5 years.

    IPCC defines lifetime for CO2 as the time required for the atmosphere to adjust to a future equilibrium state if emissions change abruptly, and gives a lifetime of 50-200 years in parentheses (Houghton et al., 1990) (William: This is phony the number). Their footnote No. 4 to their Table 1.1 explains: “For each gas in the table, except CO2, the “lifetime” is defined here as the ratio of the atmospheric content to the total rate of removal. This time scale also characterizes the rate of adjustment of the atmospheric concentrations if the emission rates are changed abruptly. CO2 is a special case since it has no real sinks, but is merely circulated between various reservoirs (atmosphere, ocean, biota). The “lifetime” of CO2 given in the table is a rough indication of the time it would take for the CO2 concentration to adjust to changes in the emissions . . .”.

    Lifetime of CO2 in the Atmosphere Based on bomb carbon-14 (in years)
    Bien & Suess [1967]: >10
    Münnich & Roether [1967]: 5.4
    Nydal [1968]: 5-10
    Young & Fairhall [1968]: 4-6
    Rafter & O’Brian [1970]: 12
    Machta (1972): 2
    Broecker et al. [1980a]: 6.2-8.8
    Stuiver [1980]: 6.8
    Quay & Stuiver [1980]: 7.5
    Delibrias [1980]: 6.0
    Druffel & Suess [1983]: 12.5
    Siegenthaler [1983]: 6.99-7.54

  113. Lester Via says:

    I misstated the IPCC report’s ocean CO2 in my previous post. Should read “the intermediate and lower depths contain more than 40 times the amount in the atmosphere”

  114. mfo says:

    Just a thought. Probably not relevant. But, Boyle’s law, Henry’s law, Charles’ law and Dalton’s law applied to scuba diving and gas are vitally important for the safety of divers.

    “At a depth of 33 feet in the water, the pressure doubles, which means gas down there is compressed to half its volume. And every regular breath of air actually takes in twice as many air molecules as on the surface. That means the air in the tank only lasts half as long.

    “Imagine taking a breath of air at a depth of 33 feet, then holding your breath and ascending to the surface. The air will expand to twice its size….” http://www.scubadiverinfo.com/2_physics.html
    http://www.idc-guide.com/physics.html

  115. Jquip says:

    Nick Stokes: “In fact, no ice age scare ever came from scientists. Lill and Revelle had it in 1958, IGY Bulletin:”

    No ice age scare?
    http://stevengoddard.wordpress.com/2013/05/21/the-1970s-ice-age-scare/

    And, of course, all you’re stating by bringing up the ghost of Revelle is that we still haven’t empirically validated things 55 years later. An actual science might have run experiments at some point during this time. Odd

  116. Gary says:

    Willis, the source data contains lat/lon coordinates and these are very different among the four cruises. Plotting all the data together mixes different regimes. Biology most certainly affects the CO2 distribution. If you continue to investigate this, look into the spacial distribution of the data.

  117. RoHa says:

    There’s CO2 in the ocean? Well, that answers the question of why the sea is boiling hot. Now for the one about pigs.

  118. F.A.H. says:

    I downloaded the data for the Lusiad cruise from 1963 and simply plotted the CO2 data as a function of sequence number, which looks like it is just a continuous time record as the ship moved along its course. Now the CO2 levels decrease dramatically between row number about 1500 and row number about 2000, going down from about 370 to 270 CO2 units. I got curious to see what was going on there so I plotted the path the ship took in Lat Long using a web mapping tool and it seems during that time, the ship began in the middle of the Arabian Sea, worked its way over to the east coast of Africa, wound its way down the coast, passing between Madagascar and Africa proper, down around Cape Elizabeth, then back up the western coast a little then out into the Atlantic. The CO2 readings decrease steadily from up in the mid Arabian Sea down the coast until the ship rounded the Cape, then they began to rise steadily. Two obvious things could need to be considered. First, on the downward trip, the ship stayed quite close to the African coast on one hand and Madagascar on the other ( or port or starboard or something). For the downward leg, the ship seemed to be within 100 or 200 km of land, whereas once it turned the corner at the cape it appears to have headed out to the open sea, in excess of 500 km out.

    Now I may have made a dumb mistake plotting the Lat Longs or something else but It seems a reasonable boat ride to take. An just looking at the changes in near shores and likely weather differences in the seas traversed, I think a lot more examination of the data is called for before anything useful could be obtained in terms of global climate and possible links between the global CO2 resident in the atmosphere versus the oceans in the large. A lot of local weather and oceanography would likely need to be taken into account. I will try to copy and paste my little Excel plot, but I am not sure if that works in a normal comment section.

    If this works here is the plot:

    Well it looks like I can’t copy and paste the plot. But it is a simple plot to do, just plot the CO2 levels versus the line (row) number (which turns out to be chronological order) and set the vertical axis minimum at around 250 or so to exclude the -999 cases.

    I didn’t look at any other data, but this suggests to me that it will take a bit of close examination of the details of each cruise to try to get anything global.

  119. F.A.H. says:

    Gary, at 4:49 PM, I just noticed your comment after I typed in my rather long one. I think I was just making your point with a little detail.

  120. E.M.Smith says:

    Fish farts and gut rocks and plants…
    Ponds and fish tanks have wide swings with light and life for gasses and pH. Diffusion and solution are smaller…

  121. Willis Eschenbach says:

    Ferdinand Engelbeen says:
    November 27, 2013 at 2:07 pm

    Willis,

    The data you plotted are only a fraction of all the data sampled at a few fixed places over the past decades and from a lot of cruises all over the oceans, together with more recent buoys set out over the oceans (still sparce) comparing air pCO2 (~ppmv) with ocean surface pCO2.
    The oldest data BTW were from a German research ship in the 1930′s, measuring pCO2 down to 2000 m depth…

    That’s good info, Ferdinand, many thanks. I’m looking for the underlying data …

    w.

  122. Greg Cavanagh says:

    It looks like the beginning of a fractal.

  123. u.k.(us) says:

    FWIW,
    Might want to talk to the whales about where the food is, they probably don’t care what their food is eating as long as it sustains it long enough for the whale to find it.
    Etc.

  124. Willis Eschenbach says:

    From Ferdinand Engelbeen’s citation, showing the pCO2 being both way above and way below the atmospheric level:

    w.

  125. fjodor says:

    I can see co2 gathering in the surface membrane in areas of outgassing. The warmer, the more outgassing, the more co2 in the surface.

    Just like opening a bottle of coke, the co2 fizzes up, gathering at the surface as foam, before being absorbed into the the air.

    Could be something similar going on here, perchance?

  126. Nick Stokes says:

    Willis Eschenbach says: November 27, 2013 at 9:20 pm
    “From Ferdinand Engelbeen’s citation, showing the pCO2 being both way above and way below the atmospheric level:”

    According to Engineering Toolbox, water going from 15° to 20°C decreases solubility by factor about 1.3. So without loss of gas, it could go from pCO2=400 to 520 μbar (ppmv). As it loses gas, the pressure will relax, but it takes time.

    The pattern of those plots looks seasonal, and fairly fast changes of order 5°C are quite possible.

  127. Willis Eschenbach says:
    November 27, 2013 at 6:44 pm

    That’s good info, Ferdinand, many thanks. I’m looking for the underlying data …

    The underlying data can be found at the CDIAC web site:
    http://cdiac.ornl.gov/oceans/datmet.html
    or from http://www.ldeo.columbia.edu/res/pi/CO2/

    The ocean research program is here:
    http://www.oco.noaa.gov/oceanCarbonNetworks.html

    About the change in pCO2 of the oceans, from Feely e.a.
    http://www.pmel.noaa.gov/pubs/outstand/feel2331/exchange.shtml

    The pCO2 in surface seawater is known to vary geographically and seasonally over a range between about 150 µatm and 750 µatm, or about 60% below and 100% above the current atmospheric pCO2 level of about 370 µatm.

    Meanwhile the atmospheric pCO2 level increased to ~400 µatm, with the ocean surface following the increase in the atmosphere with a decay rate of 1-2 years.

    Further:
    pCO2 would increase by a factor of 4 when the water is warmed from polar temperatures of about –1.9°C to equatorial temperatures of about 30°C. On the other hand, the DIC in the surface ocean varies from an average value of 2150 µmol/kg in polar regions to 1850 µmol/kg in the tropics as a result of biological processes. This change should reduce pCO2 by a factor of 4. On a global scale, therefore, the magnitude of the effect of biological drawdown on surface water pCO2 is similar in magnitude to the effect of temperature, but the two effects are often compensating. Accordingly, the distribution of pCO2 in surface waters in space and time, and therefore the oceanic uptake and release of CO2 , is governed by a balance between the changes in seawater temperature, net biological utilization of CO and the upwelling flux of subsurface waters rich in CO2

    At the upwelling places there is a constant feed of CO2 rich deep ocean waters, while near the poles there is a constant downwelling of CO2 enriched (due to the pCO2 difference) waters.
    The mid-latitudes show a pCO2 above atmosphere during a few summer months and a pCO2 below atmosphere for the rest of the year (with hardly any direct interaction with the deep oceans waters), here for Bermuda:
    http://www.biogeosciences.net/9/2509/2012/bg-9-2509-2012.pdf (Fig. 4)
    While d13C increases (as I have seen in another paper) and DIC (total inorganic carbon) decreases in summer due to increased biolife, temperature is the stronger driving factor pushing more CO2 out of the oceans, thus also decreasing DIC.
    The long term trend (Fig. 5) over 28 years shows the increase in uptake of CO2 at Bermuda, representative for the whole North Atlantic subtropical gyre.
    Similar graphs are available for Hawaii (Fig. 1):
    http://www.pnas.org/content/106/30/12235.full.pdf

  128. William Astley says:

    In reply to:

    Ferdinand Engelbeen says: November 27, 2013 at 2:07 pm
    And the whole story (William: Incorrect story. Made up story.) about the measurements and calculations is here:
    http://www.pmel.noaa.gov/pubs/outstand/feel2331/abstract.shtml
    The main reason that there are differences between ocean pCO2 and air pCO2 are:
    – temperature
    – biolife
    – migration speed
    The latter is the main problem: the migration speed of CO2 in water is very low. It is only by wind and waves that CO2 can exchange with the atmosphere at sufficient speed, depending mainly of wind speed. And at the same wind speed about in ratio with the pCO2 difference between air and seawater.

    William: The C14 bombtest data analysis contradicts the assertion that “the migration speed of CO2 in water (sic. ocean water) is very low”. The problem is the ocean data obviously indicates there is a significant release of CO2 in the equatorial region, which is an agreement with Humlum et al. August, 2012, analysis.
    http://www.false-alarm.net/
    The C14 bombtest data analysis in supports the assertion that the 1/e lifetime of the CO2 in the atmosphere is 7 years, the 50 to 200 years 1/e half life assumption in the Bern model is hokum, silly, required to prop up the CAWG hypothesis.
    http://www.false-alarm.net/wp-content/uploads/2013/06/paper1.pdf

    http://www.tech-know-group.com/papers/Carbon_dioxide_Humlum_et_al.pdf
    The phase relation between atmospheric carbon dioxide and global temperature
    Thus, summing up for the analysis of the NCDC data, changes in atmospheric CO2 is lagging 9.5-12 months behind changes in surface air temperatures calculated for the two main types of planetary surface, land and ocean, respectively. The strongest correlation (0.45) between atmospheric CO2 and NCDC temperature is found in relation to ocean surface air temperatures, suggesting a rather strong coupling from changes in ocean temperature to changes in atmospheric CO2.

    Summing up, our analysis suggests that changes in atmospheric CO2 appear to occur largely independently of changes in anthropogene emissions. A similar conclusion was reached by Bacastow (1976), suggesting a coupling between atmospheric CO2 and the Southern Oscillation. However, by this we have not demonstrated that CO2 released by burning fossil fuels is without influence on the amount of atmospheric CO2, but merely that the effect is small compared to the effect of other processes. Our previous analyzes suggest that such other more important effects are related to temperature, and with ocean surface temperature near or south of the Equator pointing itself out as being of special importance for changes in the global amount of atmospheric CO2.

    William:
    As I noted there is massive and continual release of CH4 at the spreading of the ocean floor (Nobel prize winner Thomas Gold’s deep earth hypothesis: See “The Deep Hot Biosphere: The myth of fossil fuels”, most libraries have a copy). The CH4 that is released is converted to CO2 by micro bacterial action. The source of the CH4 is from the liquid core of the earth which is expelling CH4 as it solidifies. The carbon in the CH4 is of course primordial carbon. The continual significant addition of new CO2 to the atmosphere explains why the carbonate deposited in sediments in the ocean floor (non biological, precipitates out) over geological time does not increase with C13. As land deposits of biological residue (plants) is deficient in C13 if there was not a new primordial source of carbon into the atmosphere, the ocean sediments would increase in C13 with geological time.

    One interesting side effect of the deep CH4 that is released from the core and then pushes up to the surface, is CH4 sudden release which causes some types of earthquakes. Below 60 km the mantel is plastic and cannot therefore be stressed. The very deep earthquakes are caused by the sudden release of the CH4. That explains why massive regions of the ocean floor suddenly fall as occurred in a series of recent Pacific region earthquakes. The same phenomenon explains why there were drops of up to 30 feet of land in the famous Alaskan earthquake of 1964. Supporting mantel cannot disappear to cause very, very, rapid drops in the earth’s crust, CH4 release from the mantel on the other hand will cause sudden drops. http://freepages.genealogy.rootsweb.ancestry.com/~coleen/earthquake.jpg

    The same CH4 release caused the Mississippi, New Madrid earthquake. http://www.new-madrid.mo.us/index.aspx?nid=132
    In the known history of the world, no other earthquakes have lasted so long or produced so much evidence of damage as the New Madrid earthquakes. Three of the earthquakes are on the list of America’s top earthquakes: the first one on December 16, 1811, a magnitude of 8.1 on the Richter scale; the second on January 23, 1812, at 7.8; and the third on February 7, 1812, at as much as 8.8 magnitude.

    Sand Boils
    The world’s largest sand boil was created by the New Madrid earthquake. It is 1.4 miles long and 136 acres in extent, located in the Bootheel of Missouri, about eight miles west of Hayti, Missouri. Locals call it “The Beach.” Other, much smaller, sand boils are found throughout the area. (William: Sand boils occur when there is a sudden release of CH4.)

  129. Crispin in Waterloo but really in Ulaanbaatar says:

    @Jquip says:
    >>Nick Stokes: “In fact, no ice age scare ever came from scientists. Lill and Revelle had it in 1958, IGY Bulletin:”

    >No ice age scare?
    >http://stevengoddard.wordpress.com/2013/05/21/the-1970s-ice-age-scare/

    Thanks for the link. I was just surprised to hear Nick say James Hansen (1969) was not a scientist.

  130. Greg says:

    Willis, your third rendition is the most informative where the data are colour coded , per cruise.

    It confirms my initial comment about a roughly parabolic shape. Like your initial loess but a stronger curvature.

    I still say joining the dots would be informative . Especially the dark red data looks like loop and may reflect an annual cycle traced out as the cruise progressed.

    I think the ‘parabola’ is the temp/CO2 component of the relationship.

    The strong up and down sections need isolating since there is clearly zones around 25C with either very little correlation or an extremely strong co2/SST gradient. This presumably the tropics.

    Accepting my suspicion that the red loop is seasonal, I’d say there are two primary relationships shown here. The curve and vertical line. Where this is probably going is one relationship for tropics and another elsewhere.

  131. Neo says:

    I’m curious how they managed to “null out” the emissions from the (non-nuclear) ship.

  132. John Andrews says:

    Willis, I think the graph shows that the cruises were in warmer climes. Not much else. Your stuff is always interesting.

  133. William Astley says:
    November 28, 2013 at 2:22 am

    William: The C14 bombtest data analysis contradicts the assertion that “the migration speed of CO2 in water (sic. ocean water) is very low”. The problem is the ocean data obviously indicates there is a significant release of CO2 in the equatorial region, which is an agreement with Humlum et al. August, 2012, analysis.

    William, the migration speed of CO2 in water (fresh water and seawater alike) is very low. If you don’t stirr it may take a full day for a difference in CO2 level to level out in a glass of water, but we are speaking here of 200 meter of seawater depth for the ocean mixed layer.

    Of course there is a lot of migration around the equator, partly due to upwelling, partly due to the high temperatures there. But even so, the highest upwelling at the equator is ~10 mol CO2/m2/year or 440 g/m2/year or 1.5 g CO2/m2/day. You may call that a huge migration speed, but I don’t…

    The C14 bombtest data analysis in supports the assertion that the 1/e lifetime of the CO2 in the atmosphere is 7 years

    Pettersson did find an e-fold decay rate of 14 years and the 14C decay is over 3 times shorter than the decay of an excess 12CO2, simply because the deep oceans return much lower levels of the 14C/12C ratio than for 12CO2. You did make the similar error in a previous message by looking at the residence time: that is around 5 years, but has nothing to do with the decay rate of an extra injection of 12CO2.

    The Humlum e.a. paper is proven wrong: they get conclusions about the increase of CO2 after detrending the CO2 increase. And their
    and with ocean surface temperature near or south of the Equator pointing itself out as being of special importance for changes in the global amount of atmospheric CO2.
    is proven wrong, as the increase in the atmosphere is first measured in the extratropical NH, then around the equator and then in the SH.

    I have no opinion about CH4 releases, and that is not the subject of discussion here.

  134. DocMartyn says:

    The SST are not daily averages and the highest ones are measured in early afternoon, when the wind was not blowing.
    A review of the Diurnal Sea Surface Temperature Variation is here.

    http://www.terrapub.co.jp/journals/JO/pdf/6305/63050721.pdf

    Now warming a complex buffered solution changes all sorts of constants, warm water holds less CO2 than cold water, pH will change as the pKa of buffers is temperature dependent, the equilibrium between CO2 and DIC will also be temperature dependent. These are all phenomenological; you know what is happening only by measurement, the system is too complex.

    Now life. Photosynthetic organism are able to change their depth and to also change the amount of chlorophyll they have. Their optimal cost/benefit ratio of where to be and how much chlorophyll to have depends on the diurnal light flux. At sunrise they rise to the surface and absorb the low light flux available and begin fixing CO2 (so DIC also falls). As the sun rises they become increasingly efficient until about 11:00 they are photonically saturated. Further light flux cannot be harvested, but is damaging. So they drop in depth until light flux is optimal. In early afternoon falling light flux falls and they rise again, going toward the surface until sunset.

    The upper ocean of biotically productive waters is NEVER at equilibrium with respect to CO2/DIC and the atmosphere. The biotic surface in areas of high productivity draws CO2 from the top, the atmosphere, and from below. DOC, in the form of dead organisms and excreta drops down and is converted into CO2/CH4/DIC all the way down; some making it to the bottom to be mineralized.
    In the worlds ocean deserts, there is little life and little upwelling, and the overall transfer is from atmosphere to ocean.

    Here is a nice paper showing the changes in DIC at the surface. This shows why you need to measure fluxes through the quasi-steady system, and not pretend you have an equilibrium

    http://onlinelibrary.wiley.com/doi/10.1002/jgrc.20279/pdf

  135. DocMartyn says:

    Ferdinand Engelbeen this is the actual disappearance of 14CO2 measured in Europe, and the fit if the curve corrected for dilution by man made CO2 placed in the atmosphere.

    http://i179.photobucket.com/albums/w318/DocMartyn/DecayofEuropean14C1970-2003_zpsaf4cba3c.png

    The decay time is 12.3 years. The end-point out to 2012 is first-order. The 14CO2 in the atmosphere is talking to a reservoir >30 times the amount of CO2 in the atmosphere. The only place there is that much carbon is in the oceans.

    Almost half of the CO2 added to the atmosphere by humans disappears annually. To treat this as an ‘equilibrium’, chemical transfer process between atmosphere, ocean surface and depths is quite clearly wrong. This is not chemistry, it is not geochemistry, it is biochemistry.
    The data is telling you that 14CO2 is transferred to the ocean depths, not the surface, at a rate of 0.056 y-1 and so is telling you that all the damned carbon in the atmosphere is being transferred to the depths at a rate of 0.056 y-1. If you want to know the mechanism for the speed of this transfer think of the French Guards at Waterloo.

  136. Latitude says:

    Willis Eschenbach says:
    November 27, 2013 at 9:20 pm

    From Ferdinand Engelbeen’s citation, showing the pCO2 being both way above and way below the atmospheric level:
    ========
    1995 La Nina….upwellings

  137. DocMartyn says:
    November 28, 2013 at 12:03 pm

    The problem is not the dilution of the 14CO2 bomb spike by 14CO2-free human emissions. The problem is that the deep oceans return only a fraction of the 14CO2 of the bomb spike while still returning 97% of the 12CO2 that goes into the deep oceans. See the difference between the 1960 in/outs and the 2000 in/outs:
    http://www.ferdinand-engelbeen.be/klimaat/klim_img/14co2_distri_1960.jpg
    and
    http://www.ferdinand-engelbeen.be/klimaat/klim_img/14co2_distri_2000.jpg

    Thus the decay rate of a pulse of 14CO2 is much faster than of a pulse of 12CO2 (or total CO2, as 12CO2 is near 99% 12CO2), because it is diluted (in part) by human emissions and to a large extent by deep ocean waters which did sink ~1000 years ago.

    The same happens for 13CO2. While human emissions are low in 13CO2, the human “fingerprint” is firmly diluted to ~1/3rd of what can be expected if all human emissions remained in the atmosphere. That is caused by the circulation of ~40 GtC from the deep oceans which returned after ~1000 years, having been sinking long before human emissions and bomb spikes…
    http://www.ferdinand-engelbeen.be/klimaat/klim_img/deep_ocean_air_zero.jpg

  138. DocMartyn says:

    Ferdinand Engelbeen, the end point of the 14CO2 decay curve shows you that >95% of the atmospheric CO2 has been exchanged with the deep oceans.
    Until you accept that point you cannot model anything.
    In just over 12 years half of the carbon in the atmosphere is exchanged for carbon in the deep oceans.
    When you accept this simple fact, you have a starting point to examine the effects additional CO2 addition will have on the two fluxes.

  139. Alvin says:

    So… while the ocean concentration of CO2 may seem in equilibrium, or have even higher concentrations than the air, there could be a larger “demand” as sea life and takeup of CO2 into chemical reactions of the ocean processes.

    Yet another chaotic system. What a wonderfully interesting planet we live on.

  140. DocMartyn says:
    November 28, 2013 at 11:51 am

    The SST are not daily averages and the highest ones are measured in early afternoon, when the wind was not blowing.
    A review of the Diurnal Sea Surface Temperature Variation is here.

    pCO2 measurements are from the main seawater intake, thus in general from a few meters below the waterline. The pCO2 measurements are compensated for the difference in temperature of the equilibrium equipment and the temperature at intake. See: http://www.ldeo.columbia.edu/res/pi/CO2/carbondioxide/text/Palmer_methods.pdf

    If there is no wind, then there is practically no CO2 exchange between the atmosphere and water. If there is wind, the temperature near the surface is more evenly distributed and there is less diurnal change.

    But nevertheless, it remains a complex system…

  141. DocMartyn says:
    November 28, 2013 at 12:54 pm

    Ferdinand Engelbeen, the end point of the 14CO2 decay curve shows you that >95% of the atmospheric CO2 has been exchanged with the deep oceans.
    Until you accept that point you cannot model anything.

    Yes, but that is exactly the problem of the 14CO2 decay time: that is the dilution caused by the throughput, or the residence time and that has not the slightest connection with the decay time of an extra pulse of (12)CO2 in the atmosphere…

  142. DocMartyn says:

    “that has not the slightest connection with the decay time of an extra pulse of (12)CO2 in the atmosphere…”

    Good, so you have finally agreed that we have observed an exchange of 14CO2 with the deep ocean.
    The decay profile of 14CO2 is the sum of two fluxes; the rate of transfer of 14CO2 into the deep ocean and the rate that 14CO2 from the deep ocean is transferred to the deep oceans.
    As the levels of 14CO2 are low in the deep ocean, due to the deep ocean being such a huge reservoir the back rate is small.
    With regard to total CO2, at steady state, the influx ocean to atmosphere matched he efflux ocean to atmosphere, before we began burning fossil fuel.
    At a per-industrial 535 GtC atmospheric CO2, 267.5 would go into the oceans every 12.3 years and 267.5 would come out every 12.3 years.
    At its simplest, adding a pulse of 365 GtC of 12CO2 in the pre-industrial past would bring the atmosphere up to 1000 GtC.
    500 GtC would go into the oceans in 12.3 years and and 267.5 would come out every 12.3 years. So in 12.3 years there would be 767.5 GtC left.

  143. Latitude says:

    New paper finds the oceans are a net source of CO2
    A new paper published in Deep-Sea Research finds the ocean is a net source of CO2 to the atmosphere, the opposite of claims by climate alarmists that the ocean removes CO2 from the atmosphere. According to the authors, “At the [research] site, the ocean is primarily a source of CO2 to the atmosphere, except during strong upwelling events.” The paper also notes, “Astor et al.(2005) observed the interactions between physical and biochemical parameters that lead to temporal [over time] variations in fCO2 [CO2 flux from the] sea, finding that even during periods of high production, the CO2 flux between the ocean and the atmosphere decreased but remained positive, i.e. CO2 escaped from the ocean to the atmosphere.”

    http://reef01.marine.usf.edu/sites/default/files/project/cariaco/publications/Astor_et_al_2013.pdf

  144. DocMartyn says:
    November 28, 2013 at 1:58 pm

    The problem is in your last sentence.

    The 14CO2 pulse doesn’t add any extra pressure to CO2 in the atmosphere, but 12CO2 does.

    The 14CO2 decay time shows that the equilibrium throughput is about ~22.5 GtC/year.

    Then we add a pulse of 465 GtC of 12CO2. The increased pressure increases the downwelling at the sink side with 20% and reduces the upwelling at the source side with 20%, or the output increases to 27 GtC/yr and the input reduces to 18 GtC/yr.

    The sink ratefor the extra 12CO2 then is 465 / 9 = 51.7 years

    The decay rate of the 14CO2 pulse is the decay rate of its concentration and shows the residence time for any individual CO2 molecule in the atmosphere without changing the total mass of CO2 in the atmosphere

    The decay rate of a 12CO2 pulse is the decay rate of the extra mass in the atmosphere and shows the net amount of CO2 mass that is extra absorbed by the deep oceans for the difference in mass (pressure) above the equilibrium mass (pressure).

    Two different decay rates, completely independent of each other.

    For the realistic figures, see the two carbon cycle fluxes (1960 and 2000) in a previous message.

  145. William Astley says:

    In reply to:
    Ferdinand Engelbeen says:
    November 28, 2013 at 10:05 am

    The C14 bombtest data analysis in supports the assertion that the 1/e lifetime of the CO2 in the atmosphere is 7 years
    Pettersson did find an e-fold decay rate of 14 years and the 14C decay is over 3 times shorter than the decay of an excess 12CO2, simply because the deep oceans return much lower levels of the 14C/12C ratio than for 12CO2. You did make the similar error in a previous message by looking at the residence time: that is around 5 years, but has nothing to do with the decay rate of an extra injection of 12CO2.

    William:
    Your silly assertion that anthropogenic CO2 is different that C14 in the surface ocean layer, is goofy, a nice try for warmist.

    The molecules of C14 that move into the surface ocean layer will be re-injected into the atmosphere thereby setting a plateau of C14 if that is in fact what physically happens. Observationally there is no plateau of C14, C14 continues to fall very, a very, low level which supports the assertion that there is either significant mixing of the surface ocean layer with the deep ocean or the carbon predicates out. C14 that moves in to the surface ocean layer cannot magically disappear. Now we have heard again and again that heat is hiding in the deep ocean. That is only possible if there is significant mixing of the surface ocean with deep ocean. Com’on man. You warmists need to get your stories straight.

    Now the 50 to 200 year term in the Bern equation is only valid if there is no mixing of the surface ocean layer with the deep ocean layer. If the Bern equation was correct, the C14 change with time would reach a plateau, which be due to the massive amount C14 that is trapped in the surface ocean layer.

    http://www.false-alarm.net/
    (See paper 1)
    Could someone help me out. It appears the web browsers are blocking access to paper 1.
    The paper in question explains this graph.
    http://wattsupwiththat.files.wordpress.com/2013/07/image1.png
    http://wattsupwiththat.com/2013/07/01/the-bombtest-curve-and-its-implications-for-atmospheric-carbon-dioxide-residency-time/

    I understand why the warmists have very effectively hidden the deep earth CH4 hypothesis. You are not interested in the discussing the deep earth CH4 hypothesis as it disproves your religion. Regardless, it is reality and people of science discuss reality as oppose to fantasy. People of science are curious and change their minds when observations and analysis do not support a particular theory/hypothesis.

    The New Madrid, Mississippi series of massive earthquakes were caused by a massive release of methane as was the series of Pacific deep earth earthquakes. Obviously the fossil hypothesis cannot explain a sudden increase in methane at very deep levels (what is need to explain the observation is a sudden increase in methane the fossil mechanism cannot suddenly add methane and regardless there are no organic sediments in the very deep mantel). The fossil hypothesis and cannot explain the ocean methane release and cannot explain marine hydrocarbon deposits as the amount of biological matter that reaches the bottom of the deep ocean is less than 1% (the ocean biosystem is highly evolved and efficient, the biological material that falls is eaten by marine life and marine bacteria), there is nothing left to convert to methane or to build up with time to be converted by a mythical process to liquid hydrocarbons (the reaction in question does not occur it is the same as water suddenly flowing up hill).

  146. Latitude says:
    November 28, 2013 at 3:22 pm

    The link is to a paper that describes the CO2 releases from the Cariaco Bassin: adjacent to Venezuela, tropic, warming from 25.5 – 26.5 °C over the period of interest + regular upwelling from the deep oceans. Thus a net source of CO2 for most of the time.

    Not exactly the net global CO2 uptake/release over the oceans…

  147. William Astley says:
    November 28, 2013 at 3:52 pm

    The molecules of C14 that move into the surface ocean layer will be re-injected into the atmosphere thereby setting a plateau of C14 if that is in fact what physically happens.

    William, the 14C that moves into the deep oceans is what makes the difference between 14CO2 and 12CO2 in behavior. That returns only after ~1000 years, while most 12CO2 returns in the same year. Nothing to do with 14C in the surface layer of the oceans.

    And please, the CH4 origin or fate have nothing to do with the subject of pCO2 of the oceans vs. the atmosphere…

  148. E.M.Smith says:

    Willis,
    The graph at 27Nov 9:20 is remarkably like the Unisys SST map. Especially the upwilling cold near west coastal south America. Ancient cold water being tropically warmed giving high pCO2. Where ocean gyres trap stagnation and air is decending gives low pCO2. Perhaps …

  149. DocMartyn says:

    “Ferdinand Engelbeen

    The problem is in your last sentence.

    The 14CO2 pulse doesn’t add any extra pressure to CO2 in the atmosphere, but 12CO2 does.”

    There is no pressure there is rate constant x [CO2] in one direction and rate constant x[CO2] going the other direction.
    The system has no knowledge, does not know which way entropy is, it just bleeding moves until efflux matches influx.
    Stop trying to be clever, the system isn’t clever, it system is dumb. Molecules move in both directions.

  150. Latitude says:

    Ferdinand Engelbeen says:
    November 28, 2013 at 3:52 pm
    ==
    Willis had asked how CO2 could be higher in the water than the air around it…
    …..that is an example of how

  151. William Astley says:

    In reply to:
    Ferdinand Engelbeen says:
    November 28, 2013 at 4:02 pm
    William Astley says:
    November 28, 2013 at 3:52 pm
    The molecules of C14 that move into the surface ocean layer will be re-injected into the atmosphere thereby setting a plateau of C14 if that is in fact what physically happens.
    William, the 14C that moves into the deep oceans is what makes the difference between 14CO2 and 12CO2 in behavior. That returns only after ~1000 years, while most 12CO2 returns in the same year. Nothing to do with 14C in the surface layer of the oceans.
    And please, the CH4 origin or fate have nothing to do with the subject of pCO2 of the oceans vs. the atmosphere…
    William:
    Are you pretending to be ignorant? You appear to have no understanding of what physically happens to the CO2 molecules. Where does the 1000 years come from? IPCC mythology?
    The IPCC’s Bern equation assumes there is minimal mixing of the surface ocean with the deep ocean, which explains the 173 year term.
    News Flash: There is significant mixing of the Deep ocean and the surface ocean!!! Surely Ferdinand you must have heard about this.
    Do you remember the news releases about heat hiding in the deep ocean? That is only possible if there is significant exchange of the surface ocean water with the deep ocean water. That is a game changer from the standpoint CAGW. If there is significant mixing of the surface ocean with the deep ocean deep ocean pCO2 reservoir as it contains more than 50 times more CO2 than the atmosphere makes it physically impossible for the anthropogenic CO2 to increase CO2 levels more than 5% to 10% assuming all ‘fossil’ fuel is burnt. There is an exchange of CO2 with the surface ocean and the atmosphere which will as the assumed reservoirs (atmosphere and surface ocean) are approximately equal, significantly increase the content of 14C in the surface water. The Bern equation was written with the assumption that there is limited exchange and/or precipitation of CO2 out of the surface ocean the surface ocean will continue to maintain a high level of 14C in the atmosphere (if the IPCC model was correct), that is not what is observed. IPCC model is not correct, Big surprise.

    http://wattsupwiththat.files.wordpress.com/2013/07/image1.png
    Comment:
    The Bern equation has three terms that vary with time to determine the remaining fraction of CO2 (any molecule of CO2).
    From paper 1 (assuming the equation is correct).
    “The Bern model in its pragmatic approximate form represents such a case. It describes the removal of carbon dioxide emission pulses in terms of a relaxation function (called impulse response function) involving three distinct phases governed by relaxation times of 1.2, 19, and 173 years, respectively [6]: Remaining fraction = 0.19 Exp[-t/1.2] + 0.34 Exp(-t/19] + 0.26 Exp[-t/173] + 0.22”
    William:
    The Bern equation was created to justify CAGW. It is a means to an end as opposed to a scientific based equation. I would highly recommend a read through this summary of the IPCC shenanigans concerning CO2 sinks.
    http://folk.uio.no/tomvs/esef/ESEF3VO2.pdf Carbon cycle modelling and the residence time of natural and anthropogenic atmospheric CO2: on the construction of the “Greenhouse Effect Global Warming” dogma by Tom V. Segalstad

    The Bombtest data and the Humlum paper indicate that the majority of CO2 increase in the last 50 years was due to increasing the increase in temperature of the surface ocean, not due to anthropogenic CO2 emissions.

    http://www.tech-know-group.com/papers/Carbon_dioxide_Humlum_et_al.pdf
    The phase relation between atmospheric carbon dioxide and global temperature

    The bombtest data and the Humlum paper indicate there is no CAGW problem. Humlum paper also notes that the data indicates that increases in CO2 do not cause an increase in planetary temperature which is supported by 8 other observations. There is no need to list them all, as that is kind of over kill. The CAGW parrot is dead. There is no need to beat a dead parrot.

    Regardless, phase 2 of the climate story is starting to unfold, as the planet cools which will be followed by dropping CO2 levels. It is difficult to imagine what the media, public, and scientific community will be particularly when there has been papers written about the IPCC shenanigans. I would press for firings and black balling from future research for the key instigators.

  152. DocMartyn says:
    November 28, 2013 at 5:02 pm

    DocMartyn,

    The 14CO2 pulse decay is a matter of concentration decay:
    At constant, equal in/out flux, the 14CO2 concentration decays rapidely with a ~12 years decay rate. Nothing changes with the total amount of CO2 in the atmosphere. The concentration decay rate fully depends on the height of the in- or outflux and the total mass in the atmosphere.

    The 12CO2 pulse decay is a matter of mass decay:
    At constant, equal in/out flux, nothing happens with the 12CO2 amount in the atmosphere, even if every single 12CO2 molecule is replaced with a 12CO2 molecule from another reservoir with a decay rate of ~12 years.
    But because both the influx and outflux changed with the increase in mass (pressure) above equilibrium, some of the extra 12CO2 mass is absorbed by the deep oceans. In that case, the mass decay rate depends of the difference between influx and outflux, no matter the height of influx or outflux.

    Two different decay rates without much connection between them…

  153. William Astley says:
    November 28, 2013 at 7:31 pm

    William, if you don’t read the scientific literature, you don’t know that the THC (thermohaline circulation) needs about 1000 years to return from the NE Atlantic sink places to the Pacific Ocean equatorial upwelling places (to much joy of the Chilean fishermen).
    And I have explained to you, now several times, that I do think that the Bern model is wrong, as wrong as applying the bomb test curve to the human emissions. There is a lot of exchange between the atmosphere and the deep oceans, but the 14CO2 bomb pulse decay rate is about 3 times faster than for a pulse of extra 12CO2.

    I have met Segalstad at a meeting in the European Parliament in Brussels, and had a firm discussion with him. He uses the residence time to “prove” that human emissions are not the cause of the increase in the atmosphere. But residence time and extra mass decay rate have nothing to do with each other. The same for the 14CO2 decay rate. And as repeatedly said, the Humlum paper is wrong. Its conclusions are falsified by the observations in the atmosphere.

    One failed observation is sufficient to falsify even the nicest theory…

  154. Greg says:

    Willis’ dark red colourd data:
    http://climategrog.wordpress.com/?attachment_id=713

    Seems rather pointless doing massive scatter plots without taking geolocation into account but looks worth digging into

  155. Greg says:
    November 29, 2013 at 2:23 am

    Is the middle of the delta pCO2 scale the zero difference?

  156. LucVC says:

    Since ice ages cool the ocean and the upwelling from the equatorial Pacific is the last to freeze over you should expect ice ages to have high atmospheric CO2 levels. Ice cores for sure dont show this. I dont know if there is other data that points to high CO2 levels during ice ages?

  157. William Astley says:

    In reply:

    Ferdinand Engelbeen says:
    November 29, 2013 at 1:02 am
    William Astley says:
    November 28, 2013 at 7:31 pm
    William, if you don’t read the scientific literature, you don’t know that the THC (thermohaline circulation) needs about 1000 years to return from the NE Atlantic sink places to the Pacific Ocean equatorial upwelling places (to much joy of the Chilean fishermen).
    And I have explained to you, now several times, that I do think that the Bern model is wrong, as wrong as applying the bomb test curve to the human emissions. There is a lot of exchange between the atmosphere and the deep oceans, but the 14CO2 bomb pulse decay rate is about 3 times faster than for a pulse of extra 12CO2.
    William:
    The thermohaline conveyor which was postulated by Wally Broeker to try to explain the Heinrich event cooling is a myth. There is no conveyor. There is an interchange of surface ocean water with deep ocean water, however, the ocean water does not flow like a conveyor. See information and peer reviewed papers to support that assertion.

    I see you are ignoring the implications of the heat hiding in the deep ocean hypothesis. If heat is hiding in the ocean then there must be significant mixing of the ocean surface waters with the ocean deep waters. That is the key. If there is mixing of surface ocean water with deep ocean waters then there is interchange of pCO2 with the deep ocean and with the surface ocean. As noted the deep ocean pCO2 reservoir is more than 50 times greater than the atmospheric CO2 reservoir. If there is significant mixing of the surface ocean water with the deep ocean water, the gradually anthropogenic CO2 emissions will be diluted by the massive deep ocean pCO2 reservoir.
    There is no physical reason why the gradual release of anthropogenic CO2 will not be absorbed into the deep ocean pCO2 sink as was the 14CO2. The Bern equation is not correct.
    http://wattsupwiththat.files.wordpress.com/2013/07/image1.png
    http://www.sciencedaily.com/releases/2009/05/090513130942.htm
    Cold Water Ocean Circulation Doesn’t Work As Expected
    The familiar model of Atlantic ocean currents that shows a discrete “conveyor belt” of deep, cold water flowing southward from the Labrador Sea is probably all wet.

    A 50-year-old model of ocean currents had shown this southbound subsurface flow of cold water forming a continuous loop with the familiar northbound flow of warm water on the surface, called the Gulf Stream.

    “Everybody always thought this deep flow operated like a conveyor belt, but what we are saying is that concept doesn’t hold anymore,” said Duke oceanographer Susan Lozier. “So it’s going to be more difficult to measure these climate change signals in the deep ocean.”
    “But only 8 percent of the RAFOS floats’ followed the conveyor belt of the Deep Western Boundary Current, according to the Nature report. About 75 percent of them “escaped” that coast-hugging deep underwater pathway and instead drifted into the open ocean by the time they rounded the southern tail of the Grand Banks. Eight percent “is a remarkably low number in light of the expectation that the DWBC is the dominant pathway for Labrador Sea Water,” the researchers wrote.”

    As a related aside, the North Atlantic drift current does not cause the Heinrich event cooling and is not the reason why the UK has warm winter as compared to New Brunswick, Canada.
    http://www.americanscientist.org/issues/id.999,y.0,no.,content.true,page.1,css.print/issue.aspx
    The Source of Europe’s Mild Climate, The notion that the Gulf Stream is responsible for keeping Europe anomalously warm turns out to be a myth
    http://www.atmos.washington.edu/~david/Gulf.pdf

    Is the Gulf Stream responsible for Europe’s mild winters?
    By R. SEAGER, D. S. BATTISTI, J. YIN, N. GORDON, N. NAIK, A. C. CLEMENT and M. A. CANE

  158. LucVC says:
    November 29, 2013 at 3:58 am

    Since ice ages cool the ocean and the upwelling from the equatorial Pacific is the last to freeze over you should expect ice ages to have high atmospheric CO2 levels.

    Oceans freezing over to near the equator seems to have happened once during the “snowball earth” period, although that still is controversial. The ice ages of the last millions of years were not that harsh, and sea ice was a lot more south than today, but still showing free surface/sink places quite north of the equator.
    I have read somewhere that the THC (Gulf Stream) moved north when the sea ice melted and south when the ice advanced.

  159. DocMartyn says:

    “Ferdinand Engelbeen
    The 12CO2 pulse decay is a matter of mass decay:
    At constant, equal in/out flux, nothing happens with the 12CO2 amount in the atmosphere, even if every single 12CO2 molecule is replaced with a 12CO2 molecule from another reservoir with a decay rate of ~12 years.
    But because both the influx and outflux changed with the increase in mass (pressure) above equilibrium, some of the extra 12CO2 mass is absorbed by the deep oceans. In that case, the mass decay rate depends of the difference between influx and outflux, no matter the height of influx or outflux.”

    At steady state we had 0.056 y-1 x 535 [CO2] = (CO2/DCI) 40,000 x 0.00076 y-1

    Mass action. The rate that CO2 is transferred from deep ocean into the atmosphere will be relatively constant as the 40,000 GtC isn’t going to get much bigger as a pulse of atmospheric carbon is added.

  160. DocMartyn says:
    November 29, 2013 at 5:44 am

    At steady state we had 0.056 y-1 x 535 [CO2] = (CO2/DCI) 40,000 x 0.00076 y-1

    At equilibrium, the steady state throughput of 12CO2 then is about 30 GtC/yr.
    Based on the δ13C decline of human emissions, my estimate was 40 GtC/yr. But that doesn’t matter for the theoretical calculation.

    Adding a pulse of 465 GtC into the atmosphere increases the pCO2 from ~290 μatm to ~510 μatm.

    That has consequences for the equilibrium:
    At the downwelling sites, the cold oceans have a pCO2 of minimum 150 μatm
    Assuming that the same amount of water is sinking, the amount of CO2 sinking into the deep waters then gets:
    30 GtC/yr * (510 – 150) / (290 – 150) = 77 GtC/yr
    Not completely right, as the 150 μatm doesn’t stay the same with increasing pCO2 in the atmosphere.
    At the upwelling sites, the warm oceans have a pCO2 of maximum 750 μatm.
    Assuming that the same amount of water is upwelling with the same 12CO2 concentration, the amount of 12CO2 released from the deep ocean waters gets:
    30 GtC/yr * (750 – 510) / (750 – 290) = 16 GtC/yr

    The difference in CO2 mass flow between upwelling and downwelling was zero at equilibrium, but gets ~60 GtC/yr net sink after a pulse of 465 GtC into the atmosphere.
    That gives a mass decay rate for such a pulse of 465/60 = 7.75 years.

    Much shorter than what is seen in reality, but the point is that the decay rate of a mass injection and the decay rate of a concentration injection are completely independent of each other, even if the extra mass doesn’t return from the deep oceans…

  161. Greg says:

    Ferdinand Engelbeen says:
    Is the middle of the delta pCO2 scale the zero difference?

    Yes, same scale as LHS, column 16 from the Scripps data.

  162. Greg says:

    First big rise as they passed through Panama Canal, second ramp up as they seem to navigate up between the coast of Africa and Madagascar.

  163. Greg says:

    I’ll put up some more plots later once I’ve had time to look through it. But just a quick note that first equatorial section is very near flat 28 degrees, S.Atl section fairly fairly flat 18, and Indian ocean equatorial section very flat 29 degrees C.

    First impression is that there are two opposing effects. Small changes in pCO2 in opposite direction to SST large change in CO2 to very small change in SST.

    Much stronger dependence with latitudinal change in SST which is in the same sense.

  164. DocMartyn says:

    Ferdinand, why do you think that CO2/DIC movements are due to the movements of water.
    As I have pointed out many times, we know that DIC/CO2 at the surface is converted to DOC, and that DOC falls 100 meters per day.
    The 10 m surface is always denuded of DIC/CO2 where you have life and photons. This is the rapid carbon cycle. Sending carbon down, which slowly moves upwards as CO2/CH4.

    The rate at which CO2 enters the deep ocean is 0.056 * GtC.
    There is not a saturatable limit that can be observed, or else the 14C decay curve would deviate from first order.
    Juts look at the data, and don’t have a bias as to mechanism. Describe the total system kinetically first, and do mechanistic studies later.

  165. DocMartyn says:
    November 29, 2013 at 10:42 am

    DOC dropouts from the ocean surface layer are estimated ~6 GtC/yr. DIC throughput is estimated ~40 GtC/yr.

    And we have been there before about the decrease in DIC in the surface layer: it is hardly measurable. The difference between summer and winter should be huge, but it is only 1.5% of DIC, and part of it is even from degassing in the warm months, see Fig. 4 in:
    http://www.biogeosciences.net/9/2509/2012/bg-9-2509-2012.pdf

    Juts look at the data, and don’t have a bias as to mechanism. Describe the total system kinetically first, and do mechanistic studies later.

    That is exactly what I have tried to show you, but it seems one of the most difficult points to convince people that there is a huge difference in decay rates for a turnover/concentration and an excess mass / pressure. While few have problems with the same mechanisms in finance.

    It is the difference between a turnover of capital (goods) in a factory over a year and the gain (or loss) of the same capital at the end of the year.
    The 14C pulse decay time shows you the turnover of the carbon capital investment through the natural factory over a year.
    The 12C pulse decay time shows you the gain (or loss in this case) of the carbon capital investment for the natural factory after a year.

    You can have a doubling or tripling of the turnover and still have a gain or loss of break-even of your investment…

  166. DocMartyn says:

    This is an annual average DIC profile

    http://www.azimuthproject.org/azimuth/files/dicprofile.png

    There is less DIC at the top with respect to below

    http://pmel.noaa.gov/co2/files/a16n_dic.jpg

    You can also look at an actual profile of depth and DIC with seasonal time.
    When light flux is high, the surface is warm on the steady state DIC drops by 0.3 mM at the surface. When light flux is low, the DIC at the surface is replenished from below.

    http://www.nature.com/srep/2013/130801/srep02339/images_article/srep02339-f2.jpg

    “That is exactly what I have tried to show you, but it seems one of the most difficult points to convince people that there is a huge difference in decay rates for a turnover/concentration and an excess mass / pressure”

    That is because there is no pressure.
    We know that 14C is disappearing into a kinetically infinite reservoir, RAtmos:ROcean is 50.
    The rate 14CO2 disappears is 0.056 y-1. The rate that all CO2 goes into the ocean is 0.056 y-1.
    We assume that the per-Industrial steady state the rate was the same.
    The rate of influx from the ocean into the atmosphere is almost unchanged as the increase in total carbon in the deep ocean is only slightly greater now than at pre-Industrial times.
    THERE IS NO PRESSURE.

  167. DocMartyn says:
    November 29, 2013 at 12:34 pm

    You can also look at an actual profile of depth and DIC with seasonal time.
    When light flux is high, the surface is warm on the steady state DIC drops by 0.3 mM at the surface.

    The profile gives a larger difference of 15% between the surface and the deep oceans than the seasonal difference at the surface which is only 1.5%. The difference between surface and deep oceans is partly from the dropdown of organics, but also partly from the supply of cold polar waters into the deep, containing more CO2 than the surface waters at other places.

    That is because there is no pressure.
    We know that 14C is disappearing into a kinetically infinite reservoir, RAtmos:ROcean is 50.

    DocMartyn, how do you think that the 14CO2 and the rest of the CO2 entered in the deep oceans? Not because there was a partial pressure difference? Henry’s law doesn’t work?

    If there is no partial pressure difference between atmosphere and the oceans, then there is no CO2 flux. If the partial pressure of CO2 in the atmosphere increases, then the outflux will increase and the influx will decrease. That is what governs the decay rate of a mass injection of CO2 in the atmosphere, which was not the case for the 14C injection, which simply disappears in the deep ocean mass.

    We assume that the per-Industrial steady state the rate was the same.
    The rate of influx from the ocean into the atmosphere is almost unchanged as the increase in total carbon in the deep ocean is only slightly greater now than at pre-Industrial times.

    The rate of influx from the oceans into the atmosphere depends of mainly two criteria: the concentration/amount of upwelling waters, which we may assume to be unchanged since the start of the industrial revolution, and the pCO2 difference between the ocean waters at the upwelling places and the atmosphere. The latter increased considerably over the past decades. Thus decreasing the influx considerably.
    Thus pressure is the main driving force for the mass decay rate.

  168. You have a missing piece here. Where was it measure at below or above the equator. All the Co2 is delivered to the South Hemisphere it takes 1000 years for the thermocline to recycle it to plankton and return.

    The problem now is that the southern part seems to be carbon saturated. The measurement at over 400ppm recently was above the equator; to see how bad it really is you need to measure below the equator.

    There is a scientist who wrote a report in 1957 saying there was no, repeat no problem with excess CO2 from the industrial age at that point. it had al been absorbed by the plankton. Wonder what could have changed… perhaps it’s really methane oxidation that is the problem. Methane oxidzes into CO2 and it’s pouring into our seas.

  169. DocMartyn says:

    “Henry’s law doesn’t work?”
    Now you are getting it. The surface layers where there is bioproductivity are in disequilibrium with the atmosphere and the depths.
    Henry’s law only applies to chemical equilibria; biological activity is an active process, captured short wavelengths of light power a huge dis-equilibrium; which is why we have 23% oxygen in the atmosphere.
    In addition to disequilibrium caused by life, we have the daily and annual cycles of a planet that is a sphere. At the equator hot, dense brines are formed which travel to the poles, cool, and drop down to the depths. They act as a ‘cold’ transportation system and induce a temperature profile where the bottom is cold and the top is warm. This dis-equilibrium is constant.
    [Your] 1.5% in DIC difference is also misleading, the swings in DIC content during 24 hours are even more extreme. You can measure the pCO2 above productive ocean waters and observe the daily swing of atmospheric CO2.

  170. DocMartyn says:

    “If there is no partial pressure difference between atmosphere and the oceans, then there is no CO2 flux. If the partial pressure of CO2 in the atmosphere increases, then the outflux will increase and the influx will decrease.”
    NO. NO. NO.
    There is constant influx and efflux. The fluxes are a function of the rate constants and the amounts of carbon in the two reservoirs. In a purely chemical system, if the system is at equilibrium then influx is equal to efflux; there is still exchange.
    Now if you instantaneous increase the amount of carbon in one reservoir the the flux from that reservoir increases by the ratio of size increase, double the amount of carbon and double the flux. However, the opposite flux is unaffected until you increase the concentration of carbon in this reservoir. The two reservoirs do not exchange information and agree how much to change their exchanges.

  171. RACookPE1978 says:

    Ferdinand Engelbeen says:
    November 29, 2013 at 9:27 am (replying to)

    DocMartyn says:
    November 29, 2013 at 5:44 am (and several other, similar replies about (the lack of true) CO2 equilibrium conditions)

    At steady state we had 0.056 y-1 x 535 [CO2] = (CO2/DCI) 40,000 x 0.00076 y-1

    At equilibrium, the steady state throughput of 12CO2 then is about 30 GtC/yr.
    Based on the δ13C decline of human emissions, my estimate was 40 GtC/yr. But that doesn’t matter for the theoretical calculation.

    Ah, but can we actually establish that Co2 was at a “steady state” at any given location on earth? This also questions whether CO2 was actually (globally) ever “steady” at pre-1950 levels of 280 ppm as required by the IPCC’s assumptions between 4000 BC and 1950 AD.

    Doc Martyn is getting much closer as he brings up several factors that – at ALL times – prevent ANY assumption of equilibrium conditions from being attained – at ANY time – on the real world earth. Any real world problem solution (series of opposing partial derivative of CO2 coming out of solution, and going back into solution) cannot assume CO2 is actually “constant” in the atmosphere over the “average” period of a year, changing slowly through that year as recorded by the Hawaii meters at one place at 20 degree north latitude.

    Rather, even “if” the entire atmosphere is accurately recorded at that one site, the earth’s ocean is “boiled” at the equator over a 6 hour period each day, somewhat cooler for two six hour morning and evening hours each day, and definitely cooler for each night. Further north (and south) of that hot spot, the water is equally unevenly heated each day so even my “approximation” of one “heating cycle” is incorrect at its basic level – but better than any calculation that begins at equilibrium (whole earth) changes CO2 uniformly over the whole earth, then attempts to “restore” equilibrium by balancing partial pressures.

    YOU CAN’T DO THAT. The specific CO2 partial pressure conditions change over each hour of the day, over each degree of latitude, over each day of the year; and they change further over the year as biology changes on land (strongly over the year) and over sea areas (less strongly day-to-day, but still widely variable sinks and “vents”. (A lot like surface solar exposure that way.)

    Further, the earth’s atmosphere will not EVER be in a static condition: even if it were above a flat-plate-earth-heated-on-one-side-by-an-average-sun! Rather, even such a simplification will be constantly under-shooting equilibrium and then over-shooting that “equilibrium partial pressure. there is no “thermometer” on the earth, only opposing natural forces that are NEVER in balance over time. Rather, the earth’s CO2 levls need to be viewed like a spring-supported weight oscillating over a frictionless surface. Except that frictionless mass is held between 4 or 5 or 6 springs of unequal spring constants and starting its motion from an unequal distances at an unknown speed. The net position will oscilate between the anchors, but it will never in in equilibrium since opposing forces never stop. (The opposing forces on the springs DO change over time, just as CO2 drivers change over time, but they never stop. Rather, as the measured CO2 levels in Hawaii change, the releasing forces (factors increasing CO2 release from the water, the land vegetation in fixed form, the part from Man’s release, the part from natural burns, the part from methane and permafrost and undersea and land volcanoes,e tc) do not “stop” but continue unabated (or even increasing) until the net opposing force of CO2 sinks is large enough to equal the release. But at that maximum point, the sinks are not zero, nor are they but momentarily equal to the releases. At some midpoint, we can assume there “should be” a equilibrium level, but the actual CO2 levels merely continue past it until the releases again equal sinks at the next low.

    Approximating partial pressures of CO2 into solution is correct: but the approximation cannot begin nor end with NASA-GISS/Hansen’s simplistic single-flat-plate-earth-exposed-on-side-to-the-average-sun. In that, I do disagree with Ferdinand’s conclusions.

    They are valid only for a isolated model on a lab stand inside a pressure-tight glass jar.

  172. Greg Goodman says:

    Willis seems to have gone walkabout, so I thought I’d add this graph from the most recent (1963) cruise.
    http://climategrog.wordpress.com/?attachment_id=715

    It overlays CO2 and SST plotted against position and allows us to see why there was such a jumble in the original plot by Willis. There are several regions showing different profiles. In particular the Indian Oceans stands out as behaving very differently.

    What is interesting is the approximately linear relationship between temperature and latitude over much of this range with a scaling of 4.5 deg lat / deg C with a ‘neutral’ SST of 26 degrees. This is centred on 5.5 deg north, the inter-tropical convergence zone.

    The strong excess in Indian ocean probably reflects the up-welling of cold, deep CO2 rich waters:
    http://www.ncdc.noaa.gov/paleo/ctl/images/belt.jpg
    the drop off across the region being it adapting to surface conditions by out-gassing CO2.

    This global flow pattern also matches the deficit in tropical Atlantic, where cooler surface waters from more southerly latitudes travel north and absorb CO2.

    There was also a strong deficit in the region stretching out from the Gulf of Panama into equatorial Pacific.

  173. Greg Goodman says:

    “This global flow pattern also matches the deficit in tropical Atlantic, where cooler surface waters from more southerly latitudes travel north and absorb CO2. ”

    Oops. According to the NOAA map these very waters remain warm around S.A. and are cooling as they pass into the tropics. This would make sense with the CO2 deficit , contrary to what I wrote above.

  174. Greg Goodman says:

    “Doc Matin: “…the swings in DIC during 24 hours are even more extreme”
    Yeah, I’ve noticed that too, doc ;)

  175. Andrea Silverthorne says:
    November 29, 2013 at 2:38 pm

    I am not sure what you mean and whom/what you are responding to, but the increase of CO2 is in the extra-tropical NH first, then around the equator and then in the SH:
    http://www.ferdinand-engelbeen.be/klimaat/klim_img/co2_trends_1995_2004.jpg

  176. RACookPE1978 says:
    November 29, 2013 at 9:08 pm

    Doc Martyn is getting much closer as he brings up several factors that – at ALL times – prevent ANY assumption of equilibrium conditions from being attained – at ANY time – on the real world earth.

    While there never is an equilibrium, there is no problem to establish an average CO2 level in the atmosphere: after mixing into the bulk of the atmosphere (which acts as a filter), the CO2 levels are the same everywhere on earth within 2% of full range, except near huge sources/sinks (that is the first few hundred meters over land):
    http://www.ferdinand-engelbeen.be/klimaat/klim_img/co2_trends.jpg

    The ice cores with a resolution of less than a decade to 600 years (depending of accumulation speed) show a quite nice equilibrium between CO2 and temperature:
    http://www.ferdinand-engelbeen.be/klimaat/klim_img/antarctic_cores_010kyr.jpg
    except for the last 150 years or so.

    Thus if you “filter” the data, you see that there is a quite linear releastionship between CO2 and temperature, before humans did release quite large quantities of CO2.

    Thus whatever the momentary, hourly, daily, seasonally and yearly pCO2 data in the oceans, a weighted average can be used to calculate the change in uptake/release for a change in seawater pCO2 at one side or a change in pCO2 in the atmosphere at the other side.

    Even if the average pCO2(aq) estimates are a factor 2 too low or too high, that doesn’t change the fact that the 14CO2 bomb test pulse decay rate doesn’t reflect the excess 12CO2pulse decay rate:

    The 14CO2 bomb test pulse changed the atmospheric concentration of 14CO2 going into the oceans with +100% without changing the mass flows or the return concentration.

    The 12/13CO2 human emissions pulse changed the atmospheric concentration of 12/13/14CO2 with +30% but also changed the isotopic ratio’s in the atmosphere and the mass flows, both going into the oceans and coming out of the oceans, without changing the return concentrations or isotopic compositions.

    That gives different decay times for the concentration/ratio changes as for mass changes, practically independent of each other. The 14CO2 decay is much faster than the excess mass decay…

  177. DocMartyn says:
    November 29, 2013 at 5:04 pm

    Now if you instantaneous increase the amount of carbon in one reservoir the the flux from that reservoir increases by the ratio of size increase, double the amount of carbon and double the flux. However, the opposite flux is unaffected until you increase the concentration of carbon in this reservoir. The two reservoirs do not exchange information and agree how much to change their exchanges.

    Yes I know, it is a dynamic equilibrium. But you are wrong about the opposite flux: if the pCO2 in the atmosphere increases and the concentration (pCO2) at the upwelling places remains the same, then the influx is reduced because the pCO2 difference is reduced.

    For the 14CO2 bomb spike, only the concentration of the outlflux is affected, not the total outflux or influx, neither the influx concentration.
    For the 12CO2 “human” spike, the concentration of 12CO2 is hardly affected, but that of 14CO2 and 13CO2 is, both the outflux and influx are affected , but not the influx isotopic ratio’s.

    The simultaneous 12CO2 bomb spike also affects the 14CO2 bomb spike (and 13CO2) decay by diluting the 14CO2 signal with 14CO2-free (and low 13CO2) emissions, but also by increasing the total mass uptake of the deep ocean – atmosphere exchange, as there is slightly more uptake than release.

  178. Greg Goodman says:
    November 29, 2013 at 11:34 pm

    Willis seems to have gone walkabout, so I thought I’d add this graph from the most recent (1963) cruise.
    http://climategrog.wordpress.com/?attachment_id=715

    Interesting to see how pCO2 changes with temperature and upwelling…

    There was also a strong deficit in the region stretching out from the Gulf of Panama into equatorial Pacific.

    I suppose that the drop is from the cold upwelling waters near the Chilean coast which by the trade winds is going West and slowly heating up over that traject. If I remember well from other cruises, the maximum pCO2 was reached around the Galapagos islands. But much depends of the trade winds, thus the ENSO index…

  179. Ferdinand Engelbeen says:
    November 30, 2013 at 1:50 am

    The simultaneous 12CO2 bomb spike

    I don’t think that the recent increase in total CO2 is caused by the atomic bomb tests… I am sure that it is a human 12CO2 (and some 13CO2) emissions spike…

  180. DocMartyn says:

    “But you are wrong about the opposite flux: if the pCO2 in the atmosphere increases and the concentration (pCO2) at the upwelling places remains the same, then the influx is reduced because the pCO2 difference is reduced.”

    You are describing classical kinetics; the sum of two exponentials is an exponential.
    Please, please, please think about the three components INFLUX, EFFLUX and OVERALL FLUX.
    You are confusing Influx plus efflux equals overall flux, with influx.
    Stop using mechanistic magic. Ignore the damned bias you bring to the table in the form of preconceived ways the oceans move carbon around by upwelling and downwelling. Trust the damn data.
    Look at the line shape of the 14C curve; first-order
    Look at the endpoint of the decay curve; the atmosphere is interrogating a reservoir >40 times bigger than itself.
    Look at he rate constant; the decay rate is constant even though total atmospheric carbon is increased

    CO2 exchanges with the surface of the ocean all the damned time, it does not exchange with an ‘average’ slab of ocean. It exchanges during the night and during the day. You can see CO2 disappear from the atmosphere from sun rise to mid-afternoon, then watch it rise again.
    The SST changes the partition coefficient of Argon and the Ar levels swing during the daily and annual cycles. This stuff is real, and using Henry’s law and ‘average’ SST is quite utterly dumb.

  181. Greg Goodman says:

    “You can see CO2 disappear from the atmosphere from sun rise to mid-afternoon, then watch it rise again.”

    There is a comment in the Scripp’s documentation:

    “The atmospheric air stream on the LUSIAD cruise displayed a diurnal cycle in measured CO2 mixing ratio [Waterman et al, 1996, p. 20-21], likely caused by degassing of the plastic airline when exposed to sunlight. Only nighttime air data was considered free of this effect and thus acceptable. There is an additional column containing a flag in the LUSIAD data sets, specifically a “1” for the accepted nighttime data. The listed ΔX values for non-flagged data are considered to be unreliable.”

    Here is detail snip of the hourly data. Don’t see the effect you refer to.
    http://climategrog.wordpress.com/?attachment_id=716

    Do you have evidence of this other than ” the damned bias you bring to the table in the form of preconceived ways the oceans move carbon around” ? ;)

  182. Greg Goodman says:

    That’s air-water difference , so presumably if there was a diurnal cycle it would be even clearer as one goes up and the other goes down. I don’t see their air line problem either.

  183. Bart says:

    I would hope that the takeaway from all this is a recognition that this is a complicated system, and the pat answers and narratives require a great many assumptions and conjectures to reconcile them to the data.

    It is good always to keep in mind that every untested assumption in an argument is a point of vulnerability, and when a string of assumptions is required to support an argument, the probability that they are all true and correct decreases exponentially with the number. Thus, e.g. three 50% likely assumptions are only cumulatively 12.5% likely, and ten 90% assumptions are only 35% likely. It does not generally take many assumptions before your likelihood of being correct dips below 50%, and a hypothesis which is no better than a coin toss is not a useful hypothesis.

    Any hypothesis which is supported by several assumptions is fair game to be questioned. The science is not settled.

  184. DocMartyn says:
    November 30, 2013 at 6:28 am

    think about the three components INFLUX, EFFLUX and OVERALL FLUX.

    In pre-industrial times for the deep ocean – atmosphere exchange:
    influx = efflux = overall flux (or throughput)
    and
    net flux = efflux – influx = 0

    For the 14CO2 bomb spike in 1960 (in % of the bomb spike):
    air = 100 (twice the pre-bomb level)
    influx = 100
    outflux = 45
    net flux = -55

    For the pre-industrial atmosphere/ocean system (in GtC):
    air = 290 ppmv
    influx = 40
    outflux = 40
    net flux = 0

    For the mainly 12CO2 human spike in 2000:
    air = 390 ppmv
    influx = 39.15
    outflux = 40.85
    net flux = – 1.7
    in all cases ~99% 12CO2

    The change in mass for a 30% change in atmospheric pressure caused by the extra 12CO2 is much smaller than the change in concentration of the doubling from the 14CO2 spike. Different mechanisms, different decay times…

    Look at he rate constant; the decay rate is constant even though total atmospheric carbon is increased

    The decrease of 14CO2 caused by 14C-free fossil fuels is slightly quadratic
    The decrease of 14CO2 caused by the increase in total CO2 is sllightly quadratic
    The influence of both on the linear decrease of 14CO2 due to deep ocean circulation would be hardly distinguishable from linear.

    CO2 exchanges with the surface of the ocean all the damned time

    The exchanges with the ocean surface are hardly of interest, any change in the atmosphere is followed by a 10% change in the ocean surface waters. It is the exchange with the deep ocean waters which is the main source/sink which removes or adds CO2 to the atmosphere.

    ————————–
    About the diurnal variations, these are not that huge, not even in coastal environments, where one should expect the largest (temperature/biolife) variation:
    https://www.academia.edu/2943276/Diurnal_variations_of_surface_seawater_pCO2_in_contrasting_coastal_environments

    Temperature and wind are the main driving forces in the CO2 exchanges, biolife is far less important:
    http://eprints.soton.ac.uk/358352/

  185. Greg Goodman says:

    Ferdi:
    In pre-industrial times for the deep ocean – atmosphere exchange:
    net flux = efflux – influx = 0

    For the pre-industrial atmosphere/ocean system (in GtC):
    net flux = 0

    For the 14CO2 bomb spike in 1960 (in % of the bomb spike):
    air = 100 (twice the pre-bomb level)
    influx = 100
    outflux = 45
    net flux = -55

    ===

    where do you get the net flux=0 assumptions from? Millennial-scale ice cores show significant change. How did that all happen with net zero flux?

  186. Greg Goodman says:
    November 30, 2013 at 10:19 am

    where do you get the net flux=0 assumptions from? Millennial-scale ice cores show significant change. How did that all happen with net zero flux?

    The change during a glacial-interglacial transition was ~100 ppmv over a period of ~5,000 years, or a change of 0.02 ppmv/yr or a net flux of 0.05 GtC/yr over the 40 GtC/yr in/out flux per year (if that didn’t change over glacial periods).
    A very small difference, but still significant and measurable over the full period…

    Over the whole Holocene, there was a small variation of +/- 5 ppmv, over a period of 10,000 years, again very small if one looks at the net flux changes needed to cause the change…

  187. DocMartyn says:

    How on Earth do you change the rate at which carbon departs the ocean, into the atmosphere, by adding carbon into the atmosphere?
    Do you think the molecules talk to each other and agree which way entropy is?
    A rate constant is just that, a rate, a change per unit of time. Multiply the amount of stuff and you get flux. In a binary system you have two fluxes that are independent of one another. The relative amounts of stuff change the fluxes, but not the rate constants.
    We know that the 14C went into the deep ocean at a rate of 0.056 y-1, this is the rate that CO2 goes into the deep ocean, 14C is a tracer for 12C. The atmospheric steady state is a function of influxes (ocean, land and man made fossil fuel emissions). The amount of carbon in the deep ocean is. essentially, unchanged since the industrial age and the flux of CO2 from the deep, into the atmosphere is also unchanged.
    What sets the level of atmospheric CO2 in geological time is the amount of life/dust driven mineralization of carbon in the marine sediments. This is where most of the worlds carbon is to be found in biotic organic and inorganic carbon; with the marsh forest of land long gone, unsupportable with low atmospheric [CO2].

  188. DocMartyn says:
    November 30, 2013 at 10:49 am

    How on Earth do you change the rate at which carbon departs the ocean, into the atmosphere, by adding carbon into the atmosphere?

    Form Wiki ( http://en.wikipedia.org/wiki/Henry%27s_law )

    “At a constant temperature, the amount of a given gas that dissolves in a given type and volume of liquid is directly proportional to the partial pressure of that gas in equilibrium with that liquid.”

    If you add CO2 to the atmosphere, the partial pressure of CO2(atm) increases. For a fixed water flow, concentration and surface temperature at deep ocean upwelling places, the pCO2(aq) didn’t change, but the pCO2 difference between ocean and atmosphere decreases. The influx from the oceans into the atmosphere is directly proportional to the pCO2 difference and thus the influx decreases.

    That is the difference with the 14CO2 spike: that didn’t change the influx of outflux in mass, only in concentration. The human 12CO2 spike did change the influx and outflux in mass, but hardly in concentration.

  189. DocMartyn says:

    partial pressure is just another way of saying amount; the atmosphere is the same size and the amount of carbon has increase. There is a hell of a difference between pressure and partial pressure, they have quite different meanings.

    You quote is interesting on its caveats;
    “At a constant temperature”, which only occurs at the edge of an ice pack where saline freezes and nowhere else on the planet.
    “of that gas in equilibrium with that liquid.” Whereas we always have fluctuating temperature, bioconversion of CO2 into organic matter and back again and fluctuating atmospheric CO2

  190. DocMartyn says:
    November 30, 2013 at 11:29 am

    Come on Doc, you were asking:
    How on Earth do you change the rate at which carbon departs the ocean, into the atmosphere, by adding carbon into the atmosphere?

    Well the answer is straight forward: if you add carbon to the atmosphere, the partial pressure of CO2 increases, for the same upwelling. Thus decreasing the CO2 flux from tha tupwelling.

    That there are fluctuating temperatures, biolife and (seasonal) variations of CO2 in the atmosphere is true, with or without an extra increase in the atmosphere. But still the increase of pCO2 in the atmosphere does decrease the influx of carbon, no matter the variability.

  191. DocMartyn says:
    November 30, 2013 at 11:29 am

    BTW, it doesn’t matter if the 0.0004 bar pCO2 in the atmosphere is in high vacuum or accompanied by 0.9996 bar of other molecules: as much CO2 is dissolved in water (if the water doesn’t get boiling).
    If pCO2 in the atmosphere increases to 0.0008 bar, twice the amount will dissolve in (fresh) water at equilibrium (and a lot more in seawater).

    If there is a disequilibrium, the flux will be in ratio with the disequilibrium. Thus with a higher pCO2 in water than in the atmosphere, the flux will be from water to atmosphere. If the pCO2 in the atmosphere increases, then the flux will decrease and can stop or reverse, depending of the pCO2 difference.

  192. DocMartyn says:

    ” if you add carbon to the atmosphere, the partial pressure of CO2 increases, for the same upwelling. Thus decreasing the CO2 flux from tha tupwelling”

    Pathetic. Telepathic deep water carbon.

  193. DocMartyn says:
    November 30, 2013 at 2:11 pm

    Pathetic. Telepathic deep water carbon.

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

    The pCO2 maps are combined with the solubility (s) in seawater and the kinetic forcing function, the gas transfer velocity (k), to produce the flux:
    F = k•s•ΔpCO2

    —————————————————————————————

    OK, enough for this time, will be absent a few days, so behave when I am not watching this blog…

  194. Greg Goodman says:

    DocMartyn says:

    ” if you add carbon to the atmosphere, the partial pressure of CO2 increases, for the same upwelling. Thus decreasing the CO2 flux from tha tupwelling”

    Pathetic. Telepathic deep water carbon.

    ===

    It’s not telepathic, it’s happening at the ocean surface in response to the temperature and partial pressure difference. This is well established physics. You may wish to argue about the relative importance of the biological effects but displaying bigoted ignorance of the physics is not likely to convince anyone to listen to you about the biology.

    The question you asked of Ferdinand applies in spades to you. Do you have anything but ” the damned bias you bring to the table in the form of preconceived ways the oceans move carbon around” ?

  195. DocMartyn says:

    There is a huge difference between influx, efflux and net flux. Ferdinand appears to conflate changes with net flux to changes in both influx and efflux; this is quite clearly not the case.
    You have a system where you have two equally sized reservoirs, A and B, with 1,000 molecules of dye in each, connected by a small pipe. The rate constant for movement, is 0.1 unit time-1.
    At steady state/equilibrium per unit time 100 dye molecules go from A to B and 100 dye molecules go from B to A.
    Now at t=0 add an extra 1,000 dye molecules to reservoir A.
    At t=1, the rate of moment from A to B is 2,000 x 0.1 = 200.
    At t=1, the rate of moment from B to A is STILL 1,000 x 0.1 = 100.
    So now we have 1,900 molecules in A and 1,100 in B.
    At t=2, the rate of moment from A to B is 1,900 x 0.1 = 190.
    At t=2, the rate of moment from B to A is 1,100 x 0.1 = 110.
    So now we have 1,820 molecules in A and 1,180 in B.
    The flux from reservoir B does not know or care about the size of the gradient A/B, it only cares about the rate constant and the [dye] in reservoir B. The dye molecules do not say ‘hay guys, go back there are more dyes this direction than where we have just come from’
    The net flux will give a single exponential and the endpoint will be at A=1,500 and B=1,500.
    this end point tells us about the relative size of the reservoirs.
    If the reservoir B was 9 times bigger than A, adding 1000 dyes molecules to A would give an end point of 1,100 in both reservoirs.
    If the reservoir B was 39 times bigger than A, adding 1000 dyes molecules to A would give an end point of 1,025 in both reservoirs.
    The end point of the 14CO2 decay profile tell us that reservoir B, the ocean, is >40 times bigger than reservoir A, the atmosphere.
    If the 14CO2 were only being mixed with the surface of the ocean the 14CO2 pulse would have an end point near a third of its peak.
    The 14CO2 disappearance is due to dilution of 14CO2 into the ocean void.
    Now, as chemically 14CO2 and 12CO2 are almost identical, and as the ratio of B/A is >40 (from end point). We can determine the efflux rate that ALL CO2 from the atmosphere into the ocean, 0.056 y-1. Now, the rate of influx into the atmosphere must have matched this same outflux in the past so we know that the amount of CO2 from the oceans, into the atmosphere’s is pre-industrial CO2*0.056 y-1 or 290 (ppm) x 1.91 (conversion to GtC) x 0.056 y-1 = 36 GtC.
    Note that this is about a third of the 90 GtC exchange between the atmosphere and surface layer of the ocean, which is about right given the two half-lives calculated for atmospheric 14CO2 of about 7.3 years for ocean surface and atmosphere and 12.3 years for disappearance in toto.

    The rate that CO2 is going from the deep ocean, into the atmosphere, is essentially unchanged comparing an atmospheric [CO2] of 290 ppm with one of 400 ppm, as the total amount of increase in the oceans carbon is trivial as it is such a big reservoir.

    Do not confuse a change in the overall flux in the system, with a change in both fluxes.

  196. DocMartyn says:
    December 1, 2013 at 8:01 am

    The rate that CO2 is going from the deep ocean, into the atmosphere, is essentially unchanged comparing an atmospheric [CO2] of 290 ppm with one of 400 ppm

    The error you make is that the transfers of CO2 are bidirectional at both the downwelling as the upwelling places, not unidirectional into the atmosphere at the upwelling and unidirectional into the oceans at the downwelling places.

    For a molecule CO2 in the atmosphere it doesn’t make any difference in probability that it gets absorbed by the oceans if the oceans are completely devoided of CO2 or completely saturated. In the first case, all CO2 gets into the water and none comes back, in the second case as much CO2 gets back as is captured. But the probability of being captured is exactly the same.
    If the pCO2 in the water is higher than in the atmosphere, simply more molecules escape from the liquid than enter the liquid from the atmosphere. Or reverse.

    Take the CO2 levels as number of molecules (“in” is into the atmosphere)):
    Upwelling at 500 μatm
    Downwelling 100 μatm
    Atmosphere: 300 μatm

    Upwelling: 500 in, 300 out, net 200 molecules in
    Downwelling: 100 in, 300 out, net 200 molecules out
    Overall net: 0 molecules in or out

    Now we increase CO2 in the atmosphere to 400 μatm:

    Upwelling: 500 in, 400 out, net 100 molecules in
    Downwelling: 100 in, 400 out, net 300 molecules out
    Overall net: 200 molecules out

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