phlogiston (13:29:42) :
Ferdinand Engelbeen (12:37:24)
“the increase in partial CO2 pressure in the oceans due to higher temperatures”
Now I’m confused – higher sea water temperature means MORE dissolved CO2? Does this mean that Le Chatelier’s principle is wrong?
(Le Chatelier’s Principle states that a dissolved gas (carbon dioxide in this case) always becomes less soluble with increasing temperature. One can testify to this from experience that much more gas is released from a can of soda that is opened when it is warm rather than when it is cold.)
Sorry if this confuses you: DIC (dissolved inorganic carbon) is the total amount of dissolved CO2 as CO2 + bicarbonate + carbonate in the ocean water, where pCO2 is the partial pressure of only the free CO2 in the same water. pCO2 increases as a result of higher temperature, lower pH, higher salt and/or DIC content and the CO2 tends to escape to the atmosphere, if the CO2 concentration there is lower (pCO2 there is roughly equal to ppmv, minus the water vapor content) or opposite when pCO2 of the atmosphere is higher.
Thus a higher temperature in seawater means that the free CO2 molecules in the water are more mobile and hence a higher pCO2 (without a change in total dissolved carbon) which may lead to more CO2 escape to the atmosphere…

Ferdinand Engelbeen (08:00:04) :
It is hard to catch up with all comments
Wilson (17:50:38) :
ok to recapitulate, or copy n paste:
how about the sum total of all living species on the planet, including the billions of humans. How much co2 does the sum total of animal life exhale per annum? and if this stays in the atmosphere for 100 years (or 40 years seems a new favourite) , that is a huge amount of non-fossil fuel c02 that probably surpasses fossil fuel co2, and is addition to the carbon cycle.
Ferdinand – given these factors, there should be much more c02 than there is in the atmosphere. However, these exchanges of c02 are not measured, as its an impossible task at present, and so the figures are speculation. Given the diurnal-seasonal-annual-decadal-multidecadal trends in c02 – there is a suggestion that co2 molecules can be absorbed as quickly as they are emitted, and emitted as quickly as they are absorbed.
My scepticism is not of the coefficients of Henry’s law, but on the sources and sinks of c02 which are remain relatively unknown, so that mathematics only applies to what is known, or is speculation, and an inventory of all sources of c02 isn’t measured.
My other comment was that since a 1C in ocean temperatures increase over the last 140 years at 30 metres is capable of emitting 600gt’s of c02, or else a 0.1C in SST’s can emit 6gt’s of co2, (Takahashi, 1961)then its plausible that – given sst’s have been increased over this 140 years, its probable that most c02 increase is natural, and anthropogenc co2 is still at its fraction, given the time cycle of anthropogenic emission and absorbtion.
the caveat is that these are not measured, so remain unknown.

Quoting from the Nov. 10 article:
Yet here we are, on the brink of economy crippling legislation to tackle a problem we don’t fully understand and the science is most certainly not settled on.
As much as I agree with the sentiment, I’m coming around to the notion that at heart the science doesn’t really matter to politicians, or to activists who believe in AGW. A lot of them don’t understand science in the first place. Some of them could be genuinely concerned, just based on what they’ve heard from “experts”. I think most of them see an opportunity to raise a tremendous amount of funds for all sorts of things they’d like to do. The “science” is just an excuse.
When the “science” of AGW is strongly challenged, what I’ve seen with politically connected people who were concerned about it before is they don’t care. They think it’s a problem no matter what the science says. They see “the northern ice sheet melting” and the disappearing glaciers in Glacier National Park, and don’t even get them started about “the plight of the polar bears”. They merely believe that humans are to blame for it. No real scientific evidence will convince them otherwise. They’ve believed it all along, because it ties in to an environmental belief that humans have been destroying the Earth. The “science” has merely been another arrow in their quiver, which they can use to make their arguments. For some it’s a belief that has been with them for years. They just have a new story to put on it.
It’s been disappointing for me to contemplate this idea. I’ve spent time researching and arguing about the scientific evidence with people who are alarmed about what they see, because I thought it carried significance in the argument for them. What I’ve found at bottom is most of them don’t care. WUWT posted an article a while back by Dr. Lindzen talking about how the alarmists basically take the position that the simplest model, the simplest explanation is the right one–basically adopting Occam’s Razor as a credo. That seems to be the case.
It’s essentially been an argument all along between those who have what I’d call a religious reverence for the Earth (with fundamentalist doctrines to boot) and who are basically critics of the civilization that’s been built, hoping to change it in ways that they deem to be more “environmentally friendly” and “socially responsible”, and those who have been happy about the way civilization has developed and are more pragmatic about its future development. The “science” has been used as a “prop” by one side in this argument, at least. They’ve taken advantage of the fact that science is taken as an authority in our society (something it’s not really meant to be, but that’s how it’s regarded by the public for better or worse–I think worse).
As for me I’ve been more interested in it from a skeptic’s perspective. I say fine, if we need to limit CO2 emissions let’s do it, but let’s be sure we need to do it, first. Let’s minimize our pollution (the stuff we really need to be concerned about) out of care for our home (Earth), and otherwise let economics dictate which energy strategy wins out.

Joel Shore (13:55:10) :
“Scott:
In my previous post, I said “As for your ocean calculation, I can’t tell you exactly what is wrong with it at the moment but I would suggest that you read a textbook or article that goes through such calculations.” Actually, one thing that may be part of the problem is that the oceans are best modeled as a mixed layer that has about the same amount of carbon as the atmosphere and then the deep ocean which has an amount that is about 2 orders of magnitude larger…and the exchange between the surface water and the deep ocean is pretty slow, so it is part of what forms the bottleneck (although, as I noted previously, I think the rate at which one can get calcium carbonate into the ocean to buffer the added carbonic acid due to the higher partial pressure of the CO2 gas is also an important piece of the puzzle).”
Hi Joel,
Thanks for the input. The two-layer thing is clearly where my calculation falls short–it was only a concentration calculation using the entire ocean volume and didn’t even take into consideration the thermodynamics of the CO2/bicarbonate/carbonate/calcium system. Could you reference a good review article or seminal paper on this system so I can get a better grip on it?
I am relatively new to this debate and have only been able to read bits and pieces over the last few months. Now I’m on Christmas vacation and have been reading more in depth and toying with some basic calculations to get a better grasp of things. My undergrad was in chemistry and chem eng, and my Ph.D. work is in anal chem (developing instrumentation to measure chemistry of atmospheric aerosols, ironically enough, though I know too little atmospheric chemistry to intelligently contribute on most discussions wrt that). However, most of the flows I work with are laminar, and obviously these don’t help with modeling ocean mixing (diffusion of carbonate for 10 years only nets a root(2Dt) distance of 1-2 m, clearly not important here). Thus, I still need to do quite a bit of reading to catch up with things, but unfortunately the majority of places I go to for information are far too one-sided for me to trust. 🙁
With regards to the calcium carbonate issue, I still believe that it shouldn’t be about calcium carbonate coming up from the deep ocean…calcium carbonate shouldn’t be affected much by the addition of carbonic acid, as the extra acidity (which would drive the removal of carbonate from the CaCO3) is offset by the additional carbonate (which drives the equilibrium back to the CaCO3). I would have to do some equilibrium calculations to be more certain of the exact effects. However, the ocean water still has a substantial amount of dissolved/free Ca++ (~10 mM) which can scavenge CO2/carbonate immediately with very fast kinetics. I’m only addressing the ability of the ocean to scavenge additional CO2 here, not the change in pH.
-Scott

The week that the paper was first published (early Nov 2009) was the week when the mainstream press carried the hysterical “6 degrees not 2 degrees” catastrophic warming explosion story. One of the “reasons” quoted for the new hysterical figure was that the carbon sinks were ceasing to work as usual, i.e. the opposite to what the study found. So the MSM are hardly playing catchup, but rather are playing the usual diametrically-against-the-evidence hysterical shrieking.

P Wilson (18:15:20) :
how about the sum total of all living species on the planet, including the billions of humans. How much co2 does the sum total of animal life exhale per annum? and if this stays in the atmosphere for 100 years (or 40 years seems a new favourite) , that is a huge amount of non-fossil fuel c02 that probably surpasses fossil fuel co2, and is addition to the carbon cycle
The CO2 exhaled by animals, including humans, and the decay or burning of wood is not one-way addition, it is part of the cycle: all CO2 emitted was taken away at some earlier date (months to a few years ago) from the same atmosphere. Thus it doesn’t change the CO2 level with important amounts if averaged over e.g. 10 years. On the other side, fossil fuels contain carbon from many millions of years ago, when the CO2 level was probably many times the current one. By burning oil and coal and gas, the CO2 released is really additional to the natural cycles of today.
Given the diurnal-seasonal-annual-decadal-multidecadal trends in c02 – there is a suggestion that co2 molecules can be absorbed as quickly as they are emitted, and emitted as quickly as they are absorbed
That is not true: vegetation only absorbs as much CO2 as limited by growth factors like temperature, water, nutritients,… Thus that takes time and what ultimately is sequestered as more or less permanent carbon is only a tiny fraction of what a seasonal cycle captures and releases over a year (about 2 GtC of the 60 GtC cycling). The same for the oceans: the ultimate sequestering is from the pressure difference between the atmosphere and the oceans. That sequesters only about 2 GtC from the 90 GtC flowing out and in the oceans: partly continuous from the warm equator to the cold poles, partly in/out over the seasons for the mid-latitudes. Be aware that the CO2 flows from/to the oceans are countercurrent to the flows to/from vegetation, which can be seen in the rather moderate seasonal CO2 level changes.
Thus at the end of a year some 4 GtC is really sequestered, even if much more (temperature dependent) is recycled (released and absorbed) by nature.
My other comment was that since a 1C in ocean temperatures increase over the last 140 years at 30 metres is capable of emitting 600gt’s of c02, or else a 0.1C in SST’s can emit 6gt’s of co2, (Takahashi, 1961)then its plausible that – given sst’s have been increased over this 140 years, its probable that most c02 increase is natural, and anthropogenc co2 is still at its fraction, given the time cycle of anthropogenic emission and absorbtion
One need to be careful with Henry’s law, which is only directly applicable for fresh water. Seawater contains much more CO2 than fresh water, but mainly as bicarbonate and only a very small fraction is CO2 in solution. That means that the release (or uptake) of CO2 depends mainly of two factors: the difference in partial pressure of CO2 (pCO2) between ocean surface and atmosphere and the transfer speed between the two media. The latter is the more important: wind speed gives the better indication of how much is transferred, while pCO2 mainly gives the direction of the transfer. See:
http://www.pmel.noaa.gov/pubs/outstand/feel2331/maps.shtml (Fig. 4)

Phil. (22:13:31) :
“Where do you get this from? For sea water the solubility in our current atmosphere is ~120mg/litre (which mostly exists as bicarbonate ion).”
The maximum water solubility of CO2 at atmospheric pressure and 25C is indeed 1.45 g/L as stated by _Jim, and this value comes from when the headspace is all CO2 (except for the small amount of equilibrium water vapor also in the headspace). His number is likely coming from this Wikipedia article:
http://en.wikipedia.org/wiki/Carbon_dioxide
Note that I prefer the better representation at:
http://jcbmac.chem.brown.edu/myl/hen/carbondioxideHenry.html
However, a better approach is to utilize the Henry’s law coefficient for CO2, which is 29.41 L*atm/mol at 25C. Using this value for 1 atm gives 1.496 g/L, in good agreement with _Jim’s value. Note that including the vapor pressure of H2O at 25C (23.76 torr) in the headspace lowers the partial pressure of CO2 and thus the dissolved amount changes to 1.449 g/L, fixing the above small discrepancy.
Your ~120 mg/L is on the same Wikipedia page as the 1.45g/L given above and is the ACTUAL bicarbonate concentration in the ocean (note that I use 145 mg/L in my spreadsheet, but I think that value includes carbonate and CO2 also).
I think the confusion comes from not considering the equilibria in the system. The amount of CO2 dissolved in the water depends on the amount in the air, and they are proportional. Thus, even though the fog picks up CO2 to its equilibrium concentration, it is relatively insignificant since the majority of the CO2 remains in the air. The system is more complicated than this because the dissolved CO2 is in equilibrium with bicarbonate/carbonate, and these are dominant at higher pH (fog is typically acidic). Note that this is actually why NOx/SOx is considered highly soluble. I don’t know the Henry’s law coefficients for these gases (although I wouldn’t be surprised if they’re LOWER than those for CO2!), but in reality the value is mostly pointless because the gases react with water to form the highly-soluble nitrate/nitrite or sulfate/sulfite ions, driving the equilibrium to move essentially all of the material to the water/ionic forms, giving the appearance that these gases are highly water-soluble. Theoretically, carbonate acts the same at high pH, but in practice we don’t see this because of the much higher pKa(s) of carbonate. Note that this makes doing accurate chemistry at high pH a real pain. 🙁
At 388 ppm CO2 and 25C, the equilibrium concentration of CO2 in the water is ~0.6 mg/L. However, the dominating factor for getting more into the water is the relatively high pH of ocean water driving the reaction towards the carbonate species, and as you pointed out, (bi)carbonate is present at over 100 mg/L.
Hopefully that makes things clearer and not more confusing,
-Scott

Most people assume that total atmospheric CO2 is a directly measured data set. It ain’t. It is a modeled data set. And worse, it is assumed that it should be increasing in terms of the amount, distribution, and isotope proportion relating to the anthropogenic source. This assumption puts the scientific method on its head. Maybe they call it value added data, I don’t know. But it leads and has led many down the primerose path.
If you want to create an elixir that fixes every ailment or a better trap that catches a mouse, the snake oil/mouse catching salesman creates a model that says it will do all that and more and then sells it as such. No research method involved. Just wishful thinking. The approach is a marketing approach, and a good one. Do what works, whatever it takes, to get the results we want. That is also a very good way to approach education. Describe where you want students to be academically, then apply the “do what works, whatever it takes” principal. But it ain’t the scientific method, not even when explained with equations and the word “thus”.

Well you wonderful folk of science, yes why not can we make our own electric cells for our homes? And they want to ban this innovative divice? nope no grace in this day and age should that happen by law for one thing cannot. If they try they shell out trillions of dollars to call for repairs in the damages to pre-historic land scapes noting due process of a cleaner execution of supplied power to survive and create a dollar too. will have a large litigation against all whom try to give one Crown more clout than the other private bills of support it is corrupted mechanics. I like somthing that can achieve both. not riun the two.
wait , you think this knocks the socks off this blue print I have can make water, fresh and clean like rocks from space to pressure cold energies in filtered sequences. it’s good. 240 volts to do every thing @ur momisugly 115 volts then down to 90 volts then to 60 volts then a reverse carbon like space catalistic resinonce in sound that creates a captured sound to make energy.