tag:blogger.com,1999:blog-1639738090545138933.post7144848617159238444..comments2024-02-07T10:25:05.837-05:00Comments on Home Climate Analysis: Falsification of Anthropogenic Global WarmingKevan Hashemihttp://www.blogger.com/profile/11014582378376549743noreply@blogger.comBlogger171125tag:blogger.com,1999:blog-1639738090545138933.post-19205458466330758012019-12-02T17:44:28.363-05:002019-12-02T17:44:28.363-05:00Kevan,
I recently discovered your blog after enga...Kevan,<br /><br />I recently discovered your blog after engaging a friend in climate change discussions. I've been studying the issues for some time now using my chemistry background to understand the nuances involved in this multidisciplinary field. I came to the same conclusion as you that the two main issues are how much CO2 affects global temperature and how much human emissions have increased CO2. I gained an additional insight from you and that is the possibility that the CO2 ocean reservoir is so vast that atmospheric CO2 may never double. Let me know if I am misstating your position.<br /><br />Has there been any further discussion about the appropriate use of your CaCO3-CO2-water system over the OH-CO2-water model which you attribute to mainstream climate scientists? The correctness of CO2 ocean models seems to revolve around this question. I plan to look more deeply into this without having to reinvent the wheel.<br /><br />Are you aware of papers by Ed Berry [https://edberry.com/blog/climate/climate-physics/human-co2-has-little-effect-on-the-carbon-cycle/] and Hermann Harde? [http://www.sciencepublishinggroup.com/journal/paperinfo?journalid=161&doi=10.11648/j.earth.20190803.13]Chic Bowdriehttps://www.blogger.com/profile/14171304675097928076noreply@blogger.comtag:blogger.com,1999:blog-1639738090545138933.post-57321299978779838602017-03-20T23:01:05.447-04:002017-03-20T23:01:05.447-04:00Dear Ferdinand, Thank you for your answer. I'm...Dear Ferdinand, Thank you for your answer. I'm trying to make sure I understand what you mean by "DIC change in ocean surface" and "change in the atmosphere". I'm looking at the paper you linked to. I'm embarrassed to say I don't know what pCO2 means in seawater, only what it means for a mixture of gases. The DIC change 1983-2011 was around 2020 to 2060 umol/kg, an increase of around 2%. The pCO2 change was 320 ppmv to 370 ppmv, which I guess is +50 uAtm, or 15%. If the partial pressure of CO2 in the atmosphere were 0 uAtm, what would DIC be? KevanKevan Hashemihttps://www.blogger.com/profile/11014582378376549743noreply@blogger.comtag:blogger.com,1999:blog-1639738090545138933.post-67284597230095413502017-03-16T11:11:16.439-04:002017-03-16T11:11:16.439-04:00Dear Kevan,
"controls" is big word in t...Dear Kevan,<br /><br />"controls" is big word in this case. All depends of what is actually changing. If some 100 volcanoes at the ocean bottom all together start to spew a lot of SO2, the pH will go down and CO2 will be lost to the atmosphere and the total carbon content of the oceans (DIC) would go down. At such a moment the volcanoes "control" the pH and DIC levels in the oceans. Nowadays we see the opposite happening: CO2 levels in the atmosphere increase with as result that CO2 levels in the ocean surface increase while the pH gets (slightly) lower. That is one of the reasons to conclude that the average CO2 flux is from the atmosphere into the oceans, not reverse.<br /><br />That it takes a lot of time to get everything in equilibrium is a matter of exchange/mass ratio. Most oceans have little solid CaCO3 compared to the total mass and most is at the ocean bottom (above the saturation level). As we push more CO2 into the surface, that has no direct contact with solid CaCO3, except in shallow seas and coastal. The difference is in the exchange ratio: ~50 GtC/year in/out the ocean surface for ~1000 GtC in that part of the oceans, mainly seasonal, while for the deep oceans it is ~40 GtC/year in and out between upwelling and sink places for a ~36,000 GtC reservoir.<br />There are some exchanges between the surface and the deep oceans, mostly biochemical, as are the dropouts from dead plants and animal material. But most CO2 exchanges between the atmosphere and the deep oceans bypasses the ocean surface. Thus an equilibrium change in the surface is fast, but lacks access to solid carbonates...<br /><br />There are a few stations in several oceans which measured DIC over longer periods. If you compare the CO2 change in the atmosphere over the same period with the DIC change in the ocean surface, you will see that the change in the surface is about 10% of the change in the atmosphere (fig.5):<br />http://www.biogeosciences.net/9/2509/2012/bg-9-2509-2012.pdfFerdinand Engelbeenhttp://www.ferdinand-engelbeen.be/noreply@blogger.comtag:blogger.com,1999:blog-1639738090545138933.post-725412126179121522017-03-15T13:57:18.946-04:002017-03-15T13:57:18.946-04:00I'm looking at this:
http://www.soest.hawaii....I'm looking at this:<br /><br />http://www.soest.hawaii.edu/oceanography/courses/OCN623/Spring2012/CO2pH.pdf<br /><br />The author states that CO2 "controls the pH of the ocean". Given that a solution of CO2 and water is always acidic, it seems to me a strange thing to claim that CO2 controls the pH when the pH is alkaline because of dissolved CaCO3. Reading the presentation, it sounds as if the HCO3- and CO2-2 concentrations in the ocean are dominated by CO2 gas, when they are dominated by dissolved CaCO3, which is how the acidity of the CO2 solution was overcome and reversed. So I am still confused as to why such a presentation would focus on CO2 when the ocean pH and ionic balances are controlled by CaCO3. Furthermore, the author's statement that it takes ten thousand years for the CaCO3 system to respond to changes in ocean pH seems unlikely to me. What is the author's evidence for such a statement?<br /><br />I'm looking at:<br /><br />http://onlinelibrary.wiley.com/doi/10.1029/2008GB003407/full<br /><br />and here the authors make sense to me. They are not talking about the Revelle Factor as a deviation from Henry's Law, but rather looking at how increased CO2 partial pressure changes the equilibrium for dissolved CaCO3. <br /><br />I now understand your use of the word "saturated".<br /><br />Why do you believe that the mixing of the ocean surface and the deep ocean is negligible?Kevan Hashemihttps://www.blogger.com/profile/11014582378376549743noreply@blogger.comtag:blogger.com,1999:blog-1639738090545138933.post-37360253250813675092017-03-15T11:10:08.582-04:002017-03-15T11:10:08.582-04:00Dear Kevan,
Your link is for the CO2/carbonate sy...Dear Kevan,<br /><br />Your link is for the CO2/carbonate system in soils, which is mostly the same as for the oceans, with as main difference the direct availability of solid carbonates in soils (by addition or naturally present), while for the oceans that is only true coastal or with shallow seas. However, here a similar work for the oceans, where the dissolved carbonates are part of the buffer capacity of the oceans:<br />http://www.soest.hawaii.edu/oceanography/courses/OCN623/Spring2012/CO2pH.pdf<br /><br />Anyway, all what the Revelle/buffer factor says is that a 100% change of CO2 in the atmosphere gives only a ~10% change in total C species, still 100% of dissolved "pure" CO2, but less from the other C species. That is all. As free CO2 is less than 1% of all C species in seawater, a doubling of free CO2 as in fresh water is peanuts, compared to a 10% increase of all C species...<br /><br />Some more detail:<br />http://onlinelibrary.wiley.com/doi/10.1029/2008GB003407/full<br /><br />Upwelling of deep ocean waters is mostly near land, where (trade) wind from the landside pulls deep ocean waters to the surface and sinks are near the poles as freezing water expels salts which increase the density of remaining waters... So it is a mix of winds and temperature. Not at all an important point, but if you use a multi-compartment model (including the biosphere), one can differentiate between all the different fluxes and their result...<br /><br />I used "saturated" as the time factor to reach the CO2 equilibrium between the ocean surface and the atmosphere, not the absolute end of the ocean buffer capacity: thanks to wind and waves, any change in the atmosphere (or reverse) is fast redistributed between these two (exchange rate less than a year). As both have comparable quantities of C species and the buffer factor of the oceans, the total change in the atmosphere was from ~590 to ~800 PgC (as CO2) since 1850 and in the ocean surface from ~1000 PgC to ~1030 PgC (for all inorganic C species). The latter shows up as a small increase in DIC in the ocean surface where longer time series were taken.<br /><br />As only the ocean surface is in direct, fast contact with the atmosphere, it seems to me more interesting to separate that from the deep oceans, as the latter are much larger in capacity but have a much slower exchange rate...Ferdinand Engelbeenhttp://www.ferdinand-engelbeen.be/noreply@blogger.comtag:blogger.com,1999:blog-1639738090545138933.post-51390173341195122962017-03-13T08:41:14.860-04:002017-03-13T08:41:14.860-04:00Ferdinand,
I must accept that up-welling and dow...Ferdinand, <br /><br />I must accept that up-welling and down-welling currents could dominate the exchange of CO2 between the deep ocean and the atmosphere. I accept that such exchanges take place because they motivate the growth of algae and krill that feed whales, but that's water coming up near the poles. Given that water at atmospheric pressure has greatest density at 4C, I don't see how temperature can drive the convection. But I accept that it takes place. So, there is not much use in me implementing a three-part exchange model because the exchange may not be taking place through the middle part. And in any case, the two-part model works very well. <br /><br />When you say the "surface which is easily saturated" I am not sure what you mean by "saturated". My understanding of the word "saturated" is "no longer responds to further increases", so that the surface being "saturated" with CO2 would mean "a doubling of CO2 does not increase the dissolved CO2". But that's not what you mean, judging from study of the rest of your comment. <br /><br />On the Revelle Factor, "that change is 10 times the change in CO2 mass compared to the change in fresh water" I see how the change in carbon mass in the ocean will be double the net amount of carbon absorbed from the atmosphere, because one more CO3 group is dissolved from CaCO3 for every CO2 dissolved. But I am unaware of the reactions that lead to nine CO3 being dissolved. So far as I can tell, the Revelle Factor comes from a calculation of how pure CO2 plus water would behave if you added NaOH to give it a pH of 8.2, and not from any realistic consideration of ocean chemistry. At the site by CHIP, he reproduces the CO2 and pure water ionic balance calculations, and appears to be unaware of the fact that these calculations do not apply to a saturated solution of CaCO3, nor does he seem to have realized that a solution of CO2 and water is always acidic, and to make it alkaline like the ocean, we must add something to it. What we add must not contain CO3 or else the ionic equations change dramatically and the Revelle Factor disappears.<br /><br />So I'd like to see ionic equations for the ocean that show a Revelle Factor. The equations for a saturated solution of CaCO3 and CO2 are well worked out, see below.<br /><br />http://lawr.ucdavis.edu/classes/ssc102/Section5.pdf<br /><br />That is: the Revelle Factor is a confusion generated by applying an ionic balance to the wrong solution, nothing more.<br /><br />Yours, Kevan<br /><br />Kevan Hashemihttps://www.blogger.com/profile/11014582378376549743noreply@blogger.comtag:blogger.com,1999:blog-1639738090545138933.post-56485942880805748162017-03-04T11:17:01.139-05:002017-03-04T11:17:01.139-05:00Ferdinand, Thank you for your explanation. I have ...Ferdinand, Thank you for your explanation. I have read it once and you have given me a lot to think about. I am busy this weekend, but look forward to taking the time to check the links and consider ocean up-welling. Yours, KevanKevan Hashemihttps://www.blogger.com/profile/11014582378376549743noreply@blogger.comtag:blogger.com,1999:blog-1639738090545138933.post-18938432065224973192017-03-02T16:43:35.982-05:002017-03-02T16:43:35.982-05:00One need to take into account that Henry's law...One need to take into account that Henry's law is for pure dissolved CO2 in water alone, not for bicarbonates and carbonates.<br />If you double the CO2 content in the atmosphere, that doubles free CO2 in fresh and seawater alike. For fresh water there it ends. For seawater, the chain reaction moves to more bicarbonate and more H+, but less carbonate, until a new equilibrium is reached. That is at an increase in all inorganic carbon species (DIC) about 10 times the total increase of free dissolved CO2. Thus while limited to 10% of the change in the atmosphere, that change is 10 times the change in CO2 mass compared to the change in fresh water...<br /><br />More background about the Revelle factor from chipster07 (the same person as CHIP here?) at:<br />https://chipstero7.blogspot.be/2016/12/the-revelle-factor-vs-henrys-law.html<br />Where also the Bjerrum plot is shown. That gives the relative C species at different pH. In the case of a CO2 doubling, the pH shifts a few tenths to the left (less basic), CO2(aq) from ~1 to ~2%, bicarbonates get somewhat higher and carbonates somewhat lower.<br /><br />Then what the "consensus" says:<br />"The Revelle Factor applies to the whole oceans (and not just the surface), as Archer (2005) says"<br />That is largely wrong. the ratio factor in Henry's law depends of the temperature of the liquid. In the case of CO2 in seawater that changes the solubility with 16 ppmv/K. As most of the deep oceans are isolated from direct contact with the atmosphere and simple diffusion of CO2 in calm water is extremely small, the main sinks into the deep oceans are near the poles, where the seawater temperature is around -2°C. That makes that the pressure difference between CO2 in the atmosphere (at ~400 μatm ~= ppmv) and the ocean waters (at ~150 μatm) is over 250 μatm, that pushes some 40 GtC CO2 in highly undersaturated waters into the deep oceans.<br /><br />That means that the Revelle factor plays no role in the deep coean water - atmosphere exchanges. Not now and not in the far future and the real buffer factor by far exceeds the expectations in the Bern model.<br /><br />Where Chipster07 is wrong is that he applies Henry's law to DIC, while it is only to dissolved CO2 not the other carbon species. Thus both Henry's law and the Revelle factor are at work without conflict, but at different levels: Henry's law for free CO2 alone and the Revelle factor for total carbon species. Thus the partitioning ratio of free CO2 in the oceans is not affected by the relative concentrations of DIC as the partial pressure of CO2 in the atmosphere changes (or reverse), but the relative concentrations of the other C species is affected...<br />His last chapter needs a lot of comment too, but that is not to be discussed here...<br />Ferdinand Engelbeenhttp://www.ferdinand-engelbeen.be/noreply@blogger.comtag:blogger.com,1999:blog-1639738090545138933.post-71670741422487336122017-03-02T16:42:00.241-05:002017-03-02T16:42:00.241-05:00Dear Kevan,
Indeed the deep oceans - atmosphere e...Dear Kevan,<br /><br />Indeed the deep oceans - atmosphere exchange is largely bypassing the surface: upwelling occurs mainly near land with wind from the land side (like trade winds near the equator) and downwelling is near near the poles where colder, densier waters sink in the deep. All together that is about 5% of the ocean surface each. The rest of the deep oceans is largely isolated from the surface for temperature and minerals exchanges. One exception: biolife which rests drop out of the surface and enrich the deep with organic and inorganic carbon.<br />Thus one can split the ocean-atmosphere exchanges between surface which is easily saturated and the deep oceans which need much more time to equilibrate with the atmosphere, both because of the huge mass and the relative small exchange rate of ~40 GtC/year.<br />The Bern model still is rather linear, despite the Revelle factor for the ocean surface only. That factor is only the limit (~10%) where the exchange rate is going to end. More info about the Bern model is here:<br />http://unfccc.int/resource/brazil/carbon.html<br />Where each compartment has its own decay rate for an excess caused by emissions and its own fraction of maximum uptake and some 15% remains in the atmosphere for centuries to milennia...<br />The fastest decay rate is for the ocean surface, the second for the deep oceans and the third for vegetation.<br /><br />Anyway, it is too soon to decide if the Bern model doesn't fit the real world, as the multi-decay model with limits still shows the same decay speed as a single decay rate without limits...<br /><br />The smaller increase of CO2 in the mixed layer of the oceans is in fact the real life experiment, even if there is not much sold carbonate present, with the exception of coccoliths like e-hux in all surfaces and in shallow oceans near land.<br />As the ocean surface is largely isolated from the deep oceans, there you have your oversized barrel...<br /><br /><br />More in a second part (due to size limits?)Ferdinand Engelbeenhttp://www.ferdinand-engelbeen.be/noreply@blogger.comtag:blogger.com,1999:blog-1639738090545138933.post-90739510760413521582017-03-01T20:15:01.842-05:002017-03-01T20:15:01.842-05:00Dear Ferdinand,
What a delight for me to see your...Dear Ferdinand,<br /><br />What a delight for me to see your 14CO2 distribution schematic with the cosmic ray generation included. I think you'll find that my two-reservoir model of the carbon cycle plays out the bomb-test curve rather well. See here:<br /><br />http://homeclimateanalysis.blogspot.com/2015/11/carbon-14-bomb-tests.html<br /><br />Is the Bern model linear? That is: does it follow linear differential equations for the exchange between the atmosphere and the ocean? If so, it cannot follow the bomb test carbon-14 observations and at the same time predict that our CO2 emissions will remain in the atmosphere for centuries. If it implements the Revelle Factor, then it's using non-linear differential equations.<br /><br />The top layer of the ocean is exchanging dissolved carbon with the deep ocean. In your schematic you appear to have direct exchange with the deep ocean, bypassing the top layer. I don't see how that's possible, by definition of the top layer. The carbon that dissolves in the top layer diffuses downwards. Thus I don't expect the top layer to show the same increase in dissolved carbon concentration as the atmosphere. <br /><br />Consequently, I'm puzzled by your statement that the small increase in top-layer carbon concentration implies that the Revelle factor has been proven. The way to prove the Revelle factor is to take a sealed barrel of seawater with a lump of chalk in the bottom, to keep it saturated with calcium carbonate, and pump CO2 into the air above the water. Then measure how much dissolves at equilibrium. So far as I know, this experiment has not been performed by climate scientists recently, although I did find some experiments done in the early twentieth century, and they showed the CO2 dissolving according to Henry's Law.<br /><br />Furthermore, the ionic equations used to calculate the Revelle factor are for CO2 dissolved in pure water with sodium hydroxide dissolved in it to give it an alkaline pH. If we use the ionic equations for a saturated solution of calcium carbonate, the liquid does obey Henry's law for CO2. <br /><br />Thus the Revelle factor appears to have no basis, either in ionic theory or in experiment.<br /><br />I have built a three-reservoir model of the carbon cycle, with a top-layer for the ocean. The total behavior is almost identical to the two-reservoir model, but there is a 4-year time constant for initial absorption of CO2 (and carbon 14), combined with 15-year for the deep ocean absorption. There is a rapid drop in carbon-14 down to something like 80% of initial concentration over the first 4 years, then the 15-year time constant after that.<br /><br />I could present the three-part model in another post, but I'm not sure it's worth it. I have come to the same conclusion as Arnold et al. in the paper linked below: the behavior of a two-layer ocean model does not differ significantly from the three or four or five-layer model when it comes to predicting the atmospheric concentration of carbon-14 or CO2.<br /><br />http://www.hashemifamily.com/Kevan/Climate/Dist_C14_Nature.pdf<br /><br />Thanks for your attention, KevanKevan Hashemihttps://www.blogger.com/profile/11014582378376549743noreply@blogger.comtag:blogger.com,1999:blog-1639738090545138933.post-2431314263742995912017-03-01T14:29:02.895-05:002017-03-01T14:29:02.895-05:00Kevan,
I agree that the response of any increase ...Kevan,<br /><br />I agree that the response of any increase of CO2, be it 14CO2 or 12CO2 is (more or less) the same and that the response of the (deep) ocean sinks is surprisingly linear in the past 57 years of accurate measurements.<br /><br />However, there is one problem with 14C as tracer in the atomic bomb tests: what did go into the deep oceans in 1960, at the peak of the 14C concentration, was the isotopic composition of that year, what got out of the oceans in the same year was the isotopic composition of the deep oceans, with much lower 14C content.<br />That makes that in that year about 97.5% of 12CO2 sinking in the deep oceans returned out of the upwelling zones, while only some 44% of the sinking 14CO2 did return. That makes that the decay rate for any excess 12CO2 (that is the bulk) above the steady state is much slower than any excess 14CO2... <br />Similar, but reverse, problem for 13CO2 (from human emissions).<br /><br />The calculated e-fold decay rate for 12CO2 is ~51 years or a half life time of ~35 years, much shorter than the IPCC expects, but much longer than for 14CO2.<br /><br />The IPCC uses the Bern model, where each compartiment has its own decay rate for an excess CO2 in the atmosphere (which is true), but also a saturation level, which is only true for 10% of the atmospheric change in the ocean surface, questionable for the deep oceans (zero indication until now) and non-existing for the biosphere.<br /><br />Here the fate of 12CO2/14CO2 in the different fluxes and compartiments for 1960:<br />http://www.ferdinand-engelbeen.be/klimaat/klim_img/14co2_distri_1960.jpg<br /><br />About the Revelle factor, that is empirically confirmed: The increase of CO2 in the atmosphere is known, the increase of DIC (CO2 + bi + carbonate) is measured in the ocean surface, with longer series at a few places. Here for Bermuda:<br />http://www.biogeosciences.net/9/2509/2012/bg-9-2509-2012.pdf<br />In fig.5, one can see the increase in DIC. If you compare that with the increase in the atmosphere over the same period, it is about 10%. <br />That is only the case for the ocean surface layer, which contains ~1000 GtC (the atmosphere currently ~800 GtC).<br /><br />That doesn't affect the deep ocean saturation, as these are largely isolated from the atmosphere and the main exchanges with the atmosphere are in the largest temperature differences: equator and poles, where temperature is the main driver, not chemistry...Ferdinand Engelbeenhttp://www.ferdinand-engelbeen.be/noreply@blogger.comtag:blogger.com,1999:blog-1639738090545138933.post-2828822066509421902016-11-09T20:21:33.161-05:002016-11-09T20:21:33.161-05:00CHIP, I looked up Le Chatelier's principle (an...CHIP, I looked up Le Chatelier's principle (and I don't know how you got the letter with the hat on it into your comment). I looked at the paper. It's from 1992. I did not realize that the climate models were non-linear at such an early date. Thank you for the reference. KevanKevan Hashemihttps://www.blogger.com/profile/11014582378376549743noreply@blogger.comtag:blogger.com,1999:blog-1639738090545138933.post-81314533716493211342016-11-09T11:52:10.621-05:002016-11-09T11:52:10.621-05:00“I claim the carbon cycle is linear, and by the pr...“I claim the carbon cycle is linear, and by the principle of superposition, whatever carbon-14 does in the system, carbon-12 must do also”.<br /><br />That follows logically and I agree. It is plausible that some small absorption preference would arise on the basis of different isotope frequencies, but not to the dramatic extent that the IPCC would have us believe. Regarding the Revelle Factor, there is so much confusion surrounding it. Whenever anyone tries to get to grips with the actual ‘science’ behind the Revelle Factor it always turns eventually into a kaleidoscope of technical images that have no coherent logical relationships and which leave the enquirer no clearer or better-informed. Different papers have different interpretations of how the Revelle Factor operates. The argument by Segalstad is similar to yours. He states that: “Current global carbon cycle models are made to fit the assumption that the level of CO2 in the pre-industrial atmosphere was about 280ppmv and that due to a ‘Buffer Factor’ the ocean can remove only about 10% of the atmospheric CO2 added by man’s activities (e.g. Siegenthaler and Oeschger, 1987). This ‘Buffer Factor’ was calculated by assuming that the chemical interaction of atmospheric CO2 is limited only to the reactions CO2 <-> HCO3 <-> CO32 in the 75 meters thick upper ocean layer and by neglecting other seawater species and buffer systems, and by assuming that CO2 removal will be limited to this upper layer”. He points out that: “In the current global carbon cycle models the last partial chemical reaction is neglected: CO2(g) + H2O + Ca2+(aq) <-> CaCO3(s) + 2 H+. Any additional CO2 entering the ocean from the atmosphere will have the potential of precipitating calcium carbonate according to the Principle of Le Châtelier (average ocean depth 3.8 km; average calcite saturation depth 4 km)”. The paper goes into more detail and is available to read here if you’re interested: http://www.co2web.info/np-m-119.pdf Richard Evanshttps://www.blogger.com/profile/18136791358791796099noreply@blogger.comtag:blogger.com,1999:blog-1639738090545138933.post-61247092894340934482016-11-08T20:37:10.967-05:002016-11-08T20:37:10.967-05:00CHIP,
Thank you for your encouraging comments. I...CHIP, <br /><br />Thank you for your encouraging comments. I read your quotes on the subject of the Revelle Factor, and I took a look through the Segalstad paper. <br /><br />I have a lot of respect for Henry's Law. It is widely used in chemical engineering. But consider this: suppose a gas dissolves into two species in a liquid. One species can convert back into the original gas, but the other cannot. So long as the two species remain in the same proportion, the rate at which the gas is emitted by the liquid will be proportional to the amount of gas dissolved in the liquid. There is a Henry's Law constant and Henry's Law is obeyed.<br /><br />But suppose we add acid to the solution, or make some other chemical change, and as a result, the two species no longer occur in the same proportion, but one is now rarer than the other. The rate at which the gas is emitted will change, because the concentration of the species that can emit gas has changed, even though the combined concentration of the two species remains the same. The Henry's Law constant changes, which means the solution is not obeying Henry's Law.<br /><br />The promotors of the Revelle Factor are claiming that the atmosphere-ocean system is in such a transitional state: as we increase the partial pressure of CO2, the ocean pH changes, and the distribution of carbonate ions changes rapidly, resulting in a deviation from Henry's Law.<br /><br />The question is: why do they think the ocean is in this state? It has taken me a while to figure out how they came to this conclusion, but I think I have now figured it out. I have added an update here to explain:<br /><br />http://homeclimateanalysis.blogspot.com/2015/12/carbon-14-probability-of-exchange.html<br /><br />But I'll summarize here. If you take the CO2-water system at CO2 partial pressure 0.0003 atmospheres, and nitrogen for the rest of the gas above the water, its pH is 5.8. But it follows Henry's Law. This system is not a good model of the ocean, because the ocean pH is 8.2. If, however, you add OH- to this system (by dissolving NaOH, for example) until the pH = 8.2, then hey presto, you have something with CO2 and water and the right pH and that exhibits an extraordinary transition of ionic concentrations as you increase the partial pressure of CO2, so that, far less CO2 is dissolved than you would expect from Henry's Law.<br /><br />Alternatively, you can model the top layer of the ocean as a saturated solution of CaCO3 with CO2 above at 0.0003 atmospheres, and this system, without any modification, has pH = 8.5, so it's very close to the real ocean. It also has the advantage of being realistic: the top layer of the ocean is indeed saturated with CaCO3 most of the time. This system does not undergo any dramatic changes in carbonate concentrations from 100 ppmv to 10,000 ppmv CO2 in the atmosphere, and therefore does follow Henry's Law.<br /><br />Now, why Climate Science would choose the OH-CO2-water model rather than the CaCO3-CO2-water model is anyone's guess, but I'm going with the CaCO3-CO2-water model for my carbon cycle.<br /><br />As a result, I claim the carbon cycle is linear, and by the principle of superposition, whatever carbon-14 does in the system, carbon-12 must do also.<br /><br />Yours, Kevan<br /><br /><br />Kevan Hashemihttps://www.blogger.com/profile/11014582378376549743noreply@blogger.comtag:blogger.com,1999:blog-1639738090545138933.post-89850948721139794922016-11-08T11:47:12.468-05:002016-11-08T11:47:12.468-05:00Segalstad has a good paper that explains some of t...Segalstad has a good paper that explains some of the issues with the Revelle Factor. I may as well just link it instead of quoting large chunks out of it: http://www.co2web.info/ESEF3VO2.htm Richard Evanshttps://www.blogger.com/profile/18136791358791796099noreply@blogger.comtag:blogger.com,1999:blog-1639738090545138933.post-91256355206634202772016-11-08T11:35:35.184-05:002016-11-08T11:35:35.184-05:00This comment has been removed by the author.Richard Evanshttps://www.blogger.com/profile/18136791358791796099noreply@blogger.comtag:blogger.com,1999:blog-1639738090545138933.post-10647675116230367792016-11-08T11:33:12.901-05:002016-11-08T11:33:12.901-05:00I am certainly no expert on this subject, but here...I am certainly no expert on this subject, but here are a few quotes from by blog regarding the Revelle Factor and why I think it's incorrect: <br /><br />"Take note there is no time-variable in the Revelle Factor formula (ΔPCO2ml/PCO2ml)/(ΔDIC/DIC) and the total amount of CO2 water can absorb based on that formula remains eternally constant over time until the relative concentrations of DIC change. Hence if the deep-ocean had the same DIC ratio as the surface-ocean the total amount of anthropogenic CO2 the whole ocean would absorb at equilibrium would only be 10%, in violation of Henry’s law. Once again, Henry’s law governs the solubility of gases in water and states that at a given temperature the amount of a gas dissolved in water is directly proportional to its partial pressure in the air adjacent to the solvent at equilibrium. The law can be described mathematically as: p = kHc. Where p is the partial pressure of the gas above the solute, kH is the proportionality constant (i.e. Henry’s constant) and c is the concentration of dissolved gas in the liquid. The constant of proportionality for CO2 at the average surface temperature of 15°C gives us a partitioning ratio between the atmosphere and the oceans of 1:50 respectively. If the Revelle Factor were correct and the solubility of CO2 changed as the relative concentrations of DIC shifted (which occurs when the partial pressure of CO2 changes) then kH in Henry’s law (and thus CO2’s partitioning ratio) would not be a constant for a given temperature. Note that Henry’s constant (in the equilibrium state of the law) is the ratio of the partial pressure of a gas at the liquid interface with the concentration of that gas dissolved in the liquid. Hence the constant does not change with concentration. It is a linear law. This means that the partitioning ratio of a gas (including that of CO2) is unchanged by changes to the atmospheric mass and can be multiplied up proportionally for any specified concentration in ppmv. Obviously this is in conflict with the Revelle Factor which suggests that the solubility of CO2 is affected by the relative concentrations of DIC as the partial pressure of CO2 changes".<br /><br />Regarding the Revelle Factor Bolin et al (1959) states: “Less than 10% of the excess fossil CO2 in the atmosphere should have been taken up by the mixed layer. It is therefore obvious the mixed layer acts as a bottleneck in the transport of fossil fuel CO2 into the deep sea”. This bottleneck inhibiting the transport of anthropogenic CO2 to the deep-ocean would appear to be at odds with the removal of anthropogenic 14CO2 from the atmosphere after the 1963 nuclear test-ban treaty. These tests doubled the concentration of 14CO2 in the atmosphere above its natural equilibrium level. The observations show a half-life for 14CO2 of 10-12 years (Figure 16). Equilibriation would therefore essentially be complete (by 94%) after 4 half-lifes = 40-48 years. Considering that the combined amount of carbon in the soil, vegetation and surface-ocean is ∼3,400Gts (according to the IPCC in AR5) and the total amount of carbon in the atmosphere is ∼800Gts then if such a bottleneck existed in the surface-ocean the concentration of 14CO2 in the atmosphere would have stabilized at around 23% (i.e. 800/3400). With only about 4% of 14CO2 remaining in the atmosphere today it implies that the 14CO2 has become mixed with a reservoir 25 times larger than the amount of CO2 in the atmosphere and the only place that much CO2 is known to exist (and be in exchange with the atmosphere) is in the deep-oceans. Interestingly the residence time of 14CO2 from the nuclear bomb-tests has been measured longer than that for 12CO2. This may be due to the fact that the extreme heat from the nuclear explosions ejected a large portion of 14CO2 into the stratosphere where it has a 5-8 year delay for its transfer to the troposphere".<br /><br />Fantastic posts by the way Kevan.Richard Evanshttps://www.blogger.com/profile/18136791358791796099noreply@blogger.comtag:blogger.com,1999:blog-1639738090545138933.post-62588191460406348702016-11-03T05:41:20.553-04:002016-11-03T05:41:20.553-04:00ATTP: Left the following comment on your blog, but...ATTP: Left the following comment on your blog, but don't see it there, maybe something went wrong.<br /><br />Thanks for your posts. I note that your calculation of the effect of temperature upon atmospheric CO2 is consistent with mine: you have 9C rise causing 280 ppmv to 400 ppmv, I have 12C causing a 40% increase, and the ice-core CO2-temperature measurements show 12C causing 190 ppmv to 300 ppmv.<br /><br />In your first post, you appear to be assuming that Henry's Law applies only to the CO2(aq) species, but I could be mis-reading you. To clarify, for pure water and CO2 we have:<br /><br />pCO2 = k * ([CO2(aq)] + [H2CO3] + [HCO3-] + [CO3--]) <br /><br />where k is a constant and pCO2 is the partial pressure of CO2 gas above the water, and I'm using square brackets for concentration of each species. If we dissolve CaCO2 in the water, we have have:<br /><br />pCO2 = k * ([CO2(aq)] + [H2CO3] + [HCO3-] + [CO3--] - [Ca++])<br /><br />I would call the concentration on the right side of each equation the "dissolved CO2 concentration", but you may be using that phrase in a different way, to refer only to the H2CO3 concentration, in the graph at the top of this post. I can see why you would interchange the two names: I have read a dozen chemistry chapters on this subject in the past week, and they interchange the terms H2CO3*, H2CO3, CO2(aq), Dissolved CO2, and Total Carbon Concentration. I think are lax about these terms because CO2(aq) is the dominant species in systems of pure water and CO2.<br /><br />The Revelle Factor appears to express the fact that most of the carbon in the ocean is not from atmospheric CO2, but from dissolved CaCO3 and other sources. You have the Revelle Factor around 10 for the ocean today. If the total carbon mass in the top layer of the ocean is 2000 GT, then only 200 GT of that carbon is dissolved CO2 taking part in the CO2 cycle. Is that right?<br /><br />I note that dissolved CaCO3 does not affect the rate at which CO2 molecules strike the ocean surface and are dissolved (an exothermic reaction 19 kJ/mol), nor does it change the rate at which CO2 emerges from the ocean by thermal excitation (endothermic 19 kJ/mol). The concentration of CO2 in the atmosphere will be in proportion to the mass of dissolved CO2 in the ocean. If we double the CO2 pressure in the atmosphere, the rate at which CO2 dissolves will double. Thus I see no means by which the CaCO3, nor any change in pH, can affect the linearity of the carbon cycle's diffusion equations. Do you agree? If not, can you show me some equations that express the non-linearity generated by the ocean chemistry?Kevan Hashemihttps://www.blogger.com/profile/11014582378376549743noreply@blogger.comtag:blogger.com,1999:blog-1639738090545138933.post-1401628210309440372016-11-02T21:39:45.676-04:002016-11-02T21:39:45.676-04:00Thank you. I am studying your two posts.
I have ...Thank you. I am studying your two posts. <br /><br />I have a three-layer linear carbon cycle model for you, I will play with it some more before I upload it. It turns out that the carbon mass of the top layer of the ocean (carbon-14 concentration 96% of atmospheric) is already constrained by the shape of the bomb-test response: about 350 Pg so far as I can figure, otherwise the clean-out of carbon-14 would be sharper in the first ten years. Anyway: top layer of the ocean carbon concentration rises in proportion to atmospheric, with a response time of a few years. Kevan Hashemihttps://www.blogger.com/profile/11014582378376549743noreply@blogger.comtag:blogger.com,1999:blog-1639738090545138933.post-14176891900773984102016-11-02T21:35:19.545-04:002016-11-02T21:35:19.545-04:00I'd like to see measurements of algae growth r...I'd like to see measurements of algae growth rate and CO2 concentration in air and water.Kevan Hashemihttps://www.blogger.com/profile/11014582378376549743noreply@blogger.comtag:blogger.com,1999:blog-1639738090545138933.post-38920181892124700282016-11-02T08:25:20.753-04:002016-11-02T08:25:20.753-04:00If you're interested, I wrote these posts. Th...If you're interested, I wrote these posts. The first presents the basic chemistry associated with dissolving CO2 in seawater, and the second presents some basic analysis and includes some python scripts that you can download, if you wish.<br /><br />https://andthentheresphysics.wordpress.com/2016/10/30/ocean-co2-uptake/<br /><br />https://andthentheresphysics.wordpress.com/2016/11/02/ocean-co2-uptake-part-2/...and Then There's Physicshttp://andthentheresphysics.wordpress.comnoreply@blogger.comtag:blogger.com,1999:blog-1639738090545138933.post-55469357442031638782016-10-31T12:49:28.371-04:002016-10-31T12:49:28.371-04:00Another variable in regards to the increase in CO2...Another variable in regards to the increase in CO2 is the increase in growth rates of algae and terrestrial plants. <br /><br />CO2Science.org catalogs experiments involving the growth rates of plant under increased CO2 conditions. The effects of raising CO2 by an extra 300 ppm can cause a dramatic increase in plant growth rate.<br /><br />Per an article at CO2Science, an increase in sea algae growth would increase the emission of cloud forming sulfur compounds.<br /><br />I am still reading through your site (when I can spare the time). There is a lot there to absorb. Hell_Is_Like_Newarkhttps://www.blogger.com/profile/11845488554285075902noreply@blogger.comtag:blogger.com,1999:blog-1639738090545138933.post-80242564219875927622016-10-25T19:38:51.873-04:002016-10-25T19:38:51.873-04:00I could not get the app to work either. The rabett...I could not get the app to work either. The rabett post is about the temperature-dependence of Henry's constant. I calculated that from first principles here:<br /><br />http://homeclimateanalysis.blogspot.com/2016/01/carbon-cycle-effect-of-temperature.html<br /><br />And used it to show how, according to my linear, two-part carbon system model, temperature drives the changes in CO2 concentration over the past 400k years:<br /><br />http://homeclimateanalysis.blogspot.com/2016/01/carbon-cycle-correlation-between.html<br /><br />As to the concentration of dissolved carbon increasing with partial pressure of carbon, I don't feel confident that I really understand the graphs in that UC Davis chapter. It could be that one of the constraints they put on their fourth-order ionic balance equation is that the dissolved CO2 gas (as distinct from the dissolved CaCO3 carbon) concentration increases in accordance with Henry's law at a fixed temperature, in which case the graphs themselves do not prove that this assumption is correct.Kevan Hashemihttps://www.blogger.com/profile/11014582378376549743noreply@blogger.comtag:blogger.com,1999:blog-1639738090545138933.post-74205047803331964282016-10-25T18:50:06.098-04:002016-10-25T18:50:06.098-04:00TTP: Thank you for your continued assistance. I...TTP: Thank you for your continued assistance. I'm looking at Figure 5.7 here:<br /><br />http://lawr.ucdavis.edu/classes/ssc102/Section5.pdf<br /><br />We have dissolved CaCO3 to complicate the problem. For Log(p_CO2) from -13 to +2 the dissolved CaCO3 remains constant. The sum of the three other carbon species appears to be proportional to p_CO2, to the extent that I can add log concentrations visually. There is a peak in the CO3(-2) concentration, for example, that corresponds to an dencrease in slope of the HCO2(-1) concentration as this latter species takes over being the majority species. At p_CO2 400 ppmv, or log(p_CO2) = -3.4, the slope appears to be close to 7/7 = 1.0. So it seems to me that Henry's Law applies to the partial pressure of CO2 and the amount of carbon dissolved minus the amount that we put in with CaCO3. <br /><br />What is interesting, and I'm guessing what you are interested in, is the fact that the pH of the solution changes with p_CO2.Kevan Hashemihttps://www.blogger.com/profile/11014582378376549743noreply@blogger.comtag:blogger.com,1999:blog-1639738090545138933.post-18026859991367460952016-10-25T09:39:02.127-04:002016-10-25T09:39:02.127-04:00There's an online app that does this
http://b...There's an online app that does this<br /><br />http://biocycle.atmos.colostate.edu/shiny/carbonate/<br /><br />I can't seem to get it to actually work, but the tabs include a description and the code.<br /><br />You could also read this<br /><br />http://rabett.blogspot.co.uk/2015/05/quadratic-coke.html...and Then There's Physicshttp://andthentheresphysics.wordpress.comnoreply@blogger.com