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This is a really interesting comment – only noticed it today.

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Also here is more of that pesky physicist stuff that destroys the who “greenhouse theory” completely.

Yet more physics that compares Earth and Venus to show CO2 content is irrelevant.

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Just to reinforce the ongoing main feature of my understanding of the CO2 cycle and to counter any misunderstanding from my 755.

The earth’s CO2 comings and goings are Enormously Complex and largely not accurately quantifiable..

Your ocean current outcroppings “tagged” by isotopes; have you ever seen a plume of smoke rising; can you predict where it will move from moment to moment??

When we have a full lateral and vertical system of CO2 measurement and reporting on a 1 km grid over the whole world surface; then I will agree we have something to work with.

Until then??

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The Revelle Effect (RE) to me appears to be based on the unproven assumption that the surface ocean waters (SOW) can be regarded separately from the deep oceans when taking into consideration the partitioning ratio for PCO2atm and pCO2aqueous because of the apparently long-time it takes for free CO2 to diffuse to the bottom of the oceans.

There is little migration between the ocean surface layer (the ‘mixed layer’) and the deep oceans. Most of the exchanges is via the sink flows near the poles, mainly in the NE Atlantic by the THC. It is possible to follow the mixing by tracers like the 14C bomb spike and CFC’s, both increased rapidely after WWII. See Sabine e.a. as given before:
http://www.pmel.noaa.gov/pubs/outstand/sabi2683/sabi2683.shtml

Segalstad explains it better than I ever could:

I had a quite good discussion with him at a skeptics meeting in the European parliament in Brussels. Some of his remarks were OK, some others not so.

1. Fresh water and seawater are complete different things regarding CO2. The Revelle factor stops the CO2 solution in fresh water much faster than in seawater, just because the pH is rapidely going down, pushing carbonate to bicarbonate to free CO2. Seawater is alkaline and can (and does) contain much more CO2 than fresh water.

2. Coke bottles are carbonated at 3-7 bar (depending of water temperature) within a few seconds, but the CO2 pressure in the atmosphere is 0,0004 bar. That needs a lot more time to be absorbed and migrate hundreds of meters into deeper layers than a few mm in coke.

3. A coke bottle of 2 l, or 1.5 l or 0.5 l, all will show (near) the same CO2 pressure and quantity in the air under the crown cork when shaked, while the ratio between CO2 mass in the liquids is 4:3:1. The ratio in mass doesn’t have any influence (besides delivering the necessary quantity for the increase in pressure), only the pressure at equilibrium counts.

4. The residence time of suspended POC is only 5-10 years. Again (he did that for the atmospheric residence time too), he confuses between residence time and excess decay time. Even if the residence time was less than a year, that doesn’t change one gram of organic CO2 at the surface or in the deep oceans, neither of inorganic carbon in the oceans or the atmosphere. Only when more POC is formed than destructed by bacteria in the deep, or more DIC is falling down from calciferic plankton than is redissolved in the deep, only then the CO2 levels at the surface (and indirectly in the atmosphere) will go down. Plankton growth is not influenced by increasing CO2 levels, as that is not the limiting factor in seawater (in contrast to land plants).

5. The Revelle factor is only relevant for the ocean surface, where there is a rapid equilibrium between air and water. The cold waters near the poles and the deep oceans are far from saturated, but these have a limited exchange, neither are land plants near saturation, but they have other limits. The net result is that about 10% of the emissions go into ocean surface, 20% in the deep oceans and 15% into vegetation.

References:
Neftel e.a. about the Siple ice core measurements:
http://www.biokurs.de/treibhaus/180CO2/neftel82-85.pdf

Etheridge e.a. about the Law Dome ice cores (unfortunately behind a paywall):
http://www.agu.org/pubs/crossref/1996/95JD03410.shtml

A few graphs are on my web page:
http://www.ferdinand-engelbeen.be/klimaat/jaworowski.html

Further about the CO@ measurements: wherever you measure are whatever you measure, one need to take into account that some of the measurements are outliers. For Mauna Loa, that are volcanic vents at downwind conditions (+4 ppmv) and depletion by vegetation with upwind conditions. For the South Pole, that are the harsh conditions, which cause human and equipment failures. As said before, even exhaling air in the main wind direction does increase the CO2 levels of a sample. Ever tried to open an air sample bottle within a blizzard at -80°C with your nose in the wind direction?

But there are strict criteria to include or exclude measurements for daily, monthly or yearly averages, see:
http://www.esrl.noaa.gov/gmd/ccgg/about/co2_measurements.html

But even if you use all data, including the outliers, that doesn’t make any difference in average or trend over a year:
http://www.ferdinand-engelbeen.be/klimaat/klim_img/co2_mlo_spo_raw_select_2008.jpg
Looks terrible, isn’t it? But on full scale (Mauna Loa and Samoa in this case) that looks quite different:
http://www.ferdinand-engelbeen.be/klimaat/klim_img/co2_raw_select_2008_fullscale.jpg

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You are right that many parts of the carbon cycle are hardly known, but even the largest cycle, the seasons, doesn’t change the atmospheric CO2 levels with more than 6 ppmv for 1°C change. That implies a lot of vegetation regrowth in spring (mainly the mid-latitudes NH spring) and a lot of vegetation decay in fall. Thus while Austalia had its draught and floods, that does contribute to the CO2 sources and sinks, but less than you expect…

Further, the ice cores largely differ in resolution, but for the past 150 years, the resolution is good enough to see a sudden increase or decrease of 20 ppmv sustained over 1 year, or 2 ppmv during 20 years. Even the Vostok or Dome C ice cores over the past 420 kyr or 800 kyr have sufficient resolution to show an increase of 100 ppmv over 100 years (and down again in 100 years?), as we do have now…

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That were the measurements of the calibration gases used to calibrate the equipment for CO2 measurements in the atmosphere, not actual CO2 measurements in Siowa!

*Slaps forehead* Opps. Sorry. Silly me. That was a rookie mistake. I was basing my statement on the graph below. In my eagerness I must have cited the wrong paper.

When CO2 dissolves in water, the pressure of CO2 in water and in the atmosphere must obey Henry’s Law. But in seawater, free CO2 is less than 1% of all carbon dissolved. The rest is bicarbonate and carbonate. To know how much total CO2 from the atmosphere dissolved in sawater, one combines free CO2 + bicarbonate + carbonate as DIC.
An increase of 10% CO2 in the atmosphere gives an increase of 10% of free CO2 in the ocean surface layer, but only 1% in total dissolved CO2. That is what is predicted by the Revelle factor and that is what was observed

You see, I was labouring under the (perhaps simplistically naive) impression that chemical associations such as HCO3 would have forced more CO2 down to the oceans because when you reduce the activity of CO2 in the oceans you create a disequilibrium between PCO2atm and pCO2 aqueous and this increases the driving force for transferring CO2 from the atmosphere to the oceans. Similar to how CO2 gets sequestrated by shellfish and coccolithophores or how CH4 gets converted into CO2. And since about 90% of CO2 is converted into HC03 when it reacts with H2O then this would naturally provide an enormous buffer. The Revelle Effect (RE) to me appears to be based on the unproven assumption that the surface ocean waters (SOW) can be regarded separately from the deep oceans when taking into consideration the partitioning ratio for PCO2atm and pCO2aqueous because of the apparently long-time it takes for free CO2 to diffuse to the bottom of the oceans. Hence there is a bottleneck in the atmosphere-ocean CO2 exchange. The process of CO2 diffusing to the bottom of the oceans according to the IPCC can take up to 500 years, albeit according to Segalstad POC (particular organic carbon) can sink to the bottom of the oceans in less than a year. If CO2 can diffuse to the bottom of the oceans in less than a year then there is no bottleneck and no build up of anthropogenic CO2 in the SOW and the increase in DIC must be due to natural reasons, of which there are obviously many. This is why I think that measuring an increase in DIC is not proof of the RE because CO2 is exchanging so fast between the SOW and the deep oceans.

Segalstad explains it better than I ever could:

It is appropriate as this point to add that if Bolin & Eriksson’s conditions in the last paragraph were true, carbonated beer (Bohren, 1987) and soda “pop” as we know it would be an impossibility with their “buffer” factor (see below); rain and fresh water would not show the observed equilibrium pH of 5.7 (Krauskopf, 1979); and experiments would not had shown complete isotopic equilibrium between CO2 and water in just hours, which in turn is the prerequisite for routine stable isotope analysis involving CO2 (Gonfiantini, 1981).

Experimentally it has been found that CO2 and pure water at 25 degrees C reaches 99% isotopic equilibrium after 30 hours and 52 minutes; after shaking (like wave agitation) 99% equilibrium is reached after 4 hours and 37 minutes (Gonfiantini, 1981). At 350 ppmv CO2 in the air, the equilibrium concentration of carbonic acid in pure water will be about 0.00001 molal at 25 degrees C. This chemical equilibrium is reached within 20 seconds (Stumm & Morgan, 1970). At the same temperature, at pH-values between 7 and 9, CO2 reaches 99% chemical equilibrium with water and calcium carbonate in about 100 seconds (Dreybrodt et al., 1996).

Carbonated beer, soda “pop”, and champagne are good analogues to the CO2 distribution between atmosphere and ocean. In both cases they manifest the equilibrium governed by Henry’s Law: the partial pressure of CO2 in the air will be proportional to the concentration of CO2 dissolved in water. The proportional constant is the Henry’s Law Constant, giving us a partition coefficient for CO2 between air and water of approximately 1:50 (Revelle & Suess, 1957; Skirrow, 1975; Jaworowski et al., 1992 a; Segalstad, 1996). We have all experienced that carbonated drinks contain much more (about 50 times higher concentration) CO2 than the air under the bottle cap above the carbonated water. This fact is in harsh contradiction to the Bolin & Eriksson’s “buffer” factor claim that the air will contain much more CO2 than the carbonated water, when trying to increase the partial pressure of CO2 from the assumed pre-industrial level of 290 ppmv (pressure less than 0.0003 atmospheres) to a pressure of about 3 atmospheres in the CO2 above the carbonated water in the brewed drink bottle.

Bolin & Eriksson’s “buffer” factor would give about 10 times higher CO2 concentration in air vs. sea water at about 0.0003 atmospheres CO2 partial pressure, increasing dramatically to an air/water CO2 partition coefficient of about 50:1 at a CO2 partial pressure of about 0.003 atmospheres (10 times the assumed pre-industrial level; Bacastow & Keeling, 1973; see Section 7 below for more on the “buffer” factor).

From their untenable conditions Bolin & Eriksson state: “It is obvious that an addition of CO2 to the atmosphere will only slightly change the CO2 content of the sea but appreciably effect the CO2 content of the atmosphere.” . . . “The decisive factor is instead the rate of overturning of the deep sea.” From: “the fact that the top layer of the ocean only need to absorb a small amount of CO2 from the atmosphere”, and a CO2 lifetime of 500 years for the deep ocean, Bolin & Eriksson (1959) reach the conclusion that: “an increase of the atmosphere’s content of CO2 of about 10 percent would have occurred in 1954. This value compares very favourably with the value of 10% given by Callendar (1958) as the total increase until 1955 deduced from a careful survey of all available measurements.” By over-simplifying the properties of the ocean the authors were able to construct a non-equilibrium model remote from observed reality and chemical laws, fitting the non-representative data of Callendar (1958).

At this point one should note that the ocean is composed of more than its 75 m thick top layer and its deep, and that it indeed contains organics. The residence time of suspended POC (particular organic carbon; carbon pool of about 1000 giga-tonnes; some 130% of the atmospheric carbon pool) in the deep sea is only 5-10 years. This alone would consume all possible man-made CO2 from the total fossil fuel reservoir (some 7200 giga-tonnes) if burned during the next 300 years, because this covers 6 to 15 turnovers of the upper-ocean pool of POC, based on radiocarbon (carbon-14) studies (Toggweiler, 1990; Druffel & Williams, 1990; see also Jaworowski et al., 1992 a). The alleged long lifetime of 500 years for carbon diffusing to the deep ocean is of no relevance to the debate on the fate of anthropogenic CO2 and the “Greenhouse Effect”, because POC can sink to the bottom of the ocean in less than a year (Toggweiler, 1990).

Also, when you compare the mathematical growth curves for atmospheric CO2 and human emissions the numbers for the RE simply do not add up. According to Wikipedia they explain the RE by saying: “If CO2 in the atmosphere is increased by one part per million, the CO2 in the ocean is increased by only a tenth of a part per million, because of the way that the carbon dioxide in the water is partitioned between carbonate ions and bicarbonate ions and free CO2. As additional CO2 is added, it tips the equilibrium between these three kinds of carbon dioxide, so because of the Revelle Factor, it means that you can add a large amount of CO2 to the air without adding much to the water”. This implies that about 10% of anthropogenic CO2 gets transferred down to the oceans and 90% gets added to the atmosphere upon equilibrium. According to the IPCC in AR4 anthropogenic CO2 emissions in 2007 were 29 gigatonnes corresponding to about 3.635ppm and if 10% of emissions get transferred down to the oceans as the RE implies then the atmospheric CO2 content should have increased by 3.262ppm. However the Keeling Curve tells us that the atmospheric CO2 content increased by about 2ppm. Therefore 44.8% of anthropogenic emissions must have been absorbed by the sinks, ostensibly by the ocean. The ocean appears to be absorbing significantly more than what the RE allows. How is this disparity to be explained? Either that, or there is a Missing Sink as others have postulated.

From the debated ice core (Neftel, Siple Dome), the number of samples is known and the full range is given. Where cracks were found the minima were kept, because these were in line with the median of previous and following samples at depth of the ice core.

Could you link me to these papers? I would quote an extract from Jaworowski’s paper rebutting this, but it’s very long and I can’t copy-and-paste it. Here’s the link instead: http://www.co2web.info/stoten92.pdf By the way, if you want to quote someone, just copy-and-paste the part you want to quote and put ‘b-quotes’ around the quoted passage.

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