Ocean Acidification Expansion

Guest essay by Steven Burnett

Back in July I wrote a piece that was published at Wattsupwiththat.com regarding the ocean acidification hypothesis (OA) and some of the issues I had with it. After reading the comments and more importantly reading a rebuttal I went through my equations sheet and found a few errors. Unfortunately life issues ate up a bunch of my time over the fall and winter. I have been lucky to have a break recently from tutoring and the onboarding process for one of the atomic laboratories is a bit slow so I had the time to finish this piece.

I tried to push this project out a few months ago, however some grammatical errors resulted in a request for corrections, and I decided to do an entire rewrite. I chose to delay the submission because of a somewhat disconcerting conclusion I came to after reworking the equations and adding some of the peer reviewed studies. The findings are contained in the second section of the essay, but the synopsis is there is no real way to determine if the increase in atmospheric CO2 is mostly anthropogenic. The same equilibrium relationship that drives the doom and gloom predictions of rising atmospheric CO2, works in reverse if the pH drops below the atmospheric equilibrium value.

This may be one of the strongest arguments against an industrial impact on atmospheric CO2 and for natural forces affecting atmospheric CO2.

It would offer a plausible mechanism between the rise in temperature and the subsequent rise in CO2, even accounting for the lag period as a process response. There are still a variety of calculations that need to be performed but it does offer a reasonable null hypothesis to the idea of anthropogenic emissions being the majority of factor in atmospheric CO2

1. My Mistakes

For large complex systems I typically use PTC’s MathCAD for its excellent ability to display equations in true math format, store variables and carry units. The GUI for this program is simply amazing.  The original equation set that I used in the essay was generally correct, however it was developed to look at OA in response to a forum debate I was observing. Because I have yet to receive my big oil check (maybe it bounced), I developed the set as a back of the envelope calculation to evaluate, presented my results and let some of the engineers check my math.  It turns out there were some errors they did not catch, so when I wrote this essay and reviewed the equation sheet, it was only a cursory glance, after all it had passed a “peer review”. Here’s what I found on a more thorough investigation.

I mentioned the EPA value for change on ocean temperature as 1.5-1.75 C when in fact it was Fahrenheit. I assumed that all reputable agencies worked with SI units but I was wrong. Truthfully henry’s law constant corrections are not particularly necessary until you approach temperature variances of about 10C. This value was only researched and correction included because I saw a sceptic trying to claim the change in the henry’s law coefficient was what was responsible for changes in atmospheric CO2 concentrations, this is simply false the thermal variance is too small to significantly impact the direction of CO2 flux.

The second issue I found was a complete user error. When entering the unit set I wanted for atmospheric pressure I was thinking in PSI, not sure why I just was, however in the equation I defined it as atmospheres. Thus the partial pressure of CO2 in my systems of equations was increased by a factor of about 15. When evaluating answers we have a general range of value we find acceptable.  The multiplication factor produced a value of .001 for pH which was lower than expected but not so low as to automatically reject it. When the error was removed the calculated pH on my equation set fell to a change of about .0001 which is far too low to be reasonable.

So what happened? In short I took a shortcut which is mathematically invalid. Below are the four main equilibrium equations regarding an aqueous system of CO2.

image

The first equation is henry’s law which represents the equilibrium relationship between the partial pressure of CO2 and dissolved CO2 in water.  The second equation describes the hydration equilibrium between dissolved CO2 and carbonic acid. The third equation describes the first dissociation constant of H2CO3 and bicarbonate. The last equation describes the relationship between carbonate and bicarbonate. They don’t look drastically different than the modified versions I was using in the original essay.

The fundamental difference lies in the concentration of hydrogen atoms which is not visible in my original set.  I was focused on the relationship between how concentrations of the carbonic substance influence the concentrations of the others.  So I removed the hydrogen Ion concentration and inferred it from the change in in concentration of the respective dissociated Ions. I inadvertently set the value of my equilibrium equations to a hydrogen ion concentration of 1. To speak more plainly I didn’t realize I was performing my calculations in a system with an assumed pH of 0.  I apologize for my mistake.

The very heart of the issue, and the core of my skepticism with most climatological finger pointing is the lack of data. There are no preindustrial pH measurements (more on this later). Without pre-industrial pH or for that matter any one of the other chemical species we cannot easily determine the equilibrium concentrations of any of the ions. It is also feasible to find a reasonable approximation through some fairly tedious algebra, which I attempted, found a close approximation but likely missed a step in the 3-6 pages of mixed success and derivations. It resolves to a cubic function, from which a root can be found and a second set of equations solved.  I will even set up the equations for those who want to play with them.

image

If we assume the major contributor to hydrogen ion concentration is atmospheric CO2, and if all resultant ions are tied to this then for each H2CO3 that dissociates, the concentration of hydrogen will increased by a total value of x1 which is the same increase in HCO3 concentration. For each subsequent dissociation of HCO3 the concentration of CO3 and hydrogen ions will increase by a total of x2. Thus the total hydrogen will be equal to the initial value plus x1 and x2, x1 and x2 can be negative.  The zeroes in the ion concentration designate an initial starting point and the t designates the target period to solve for, enjoy.

That being said we can much more easily approximate a comparable solution by making one more assumption.  If the first dissociation is the dominant factor in the production of hydrogen ions, which it is ka1=2.5*10-4and ka2=4.69*10-11, then we can assume that the x2 contribution to hydrogen ions is essentially 0.  This gives us a beautiful quadratic which is very easily solved as seen in equation 7 and then 8.

image

Had I read through the entirety of the Wikipedia and seen the line at the end suggesting that solution I would have saved a few headaches, and trees. I did however come to the same conclusion independently

Under these conditions we can see the relative changes in concentration of the various ionic species. As more CO2 enters the system carbonic acid goes up, hydrogen ion concentration goes up and bicarbonate ions increase at the same rate.

However referencing the carbonate ion concentration, as the relative change in hydrogen ions is much larger than the change in bicarbonate, thus carbonate levels will drop. For example if I doubled the concentration of hydrogen ions, the concentration of carbonate ions will necessarily drop by half to maintain the equilibrium. An increase in concentration of 1*10^-8.2 hydrogen ions is relatively larger than the same increase at a base concentration in the range of 1*10^-4.

So what does this prove? Sadly nothing. This system of equations only describes sterile, filtered seawater in a flask and holds about the same significance on the results as spherical chickens in a vaccuum.

2. What is the model missing?

Unfortunately there are a large number of factors which are simply not accounted for in a flask hypothesis. There is of course the change in relative concentrations of important chemical species from things like biological function, sequestration, or other natural phenomena. These factors mean the flask model only applies at the boundary layer, a hypothetical infinitely thin slice that represents the boundary between the oceans and the atmosphere.

Phytoplankton will consume oceanic CO2 for photosynthesis. Other microscopic organisms will produce different compounds resulting from various metabolic pathways. Many of which can influence pH, such as ammonia, acetic acid, urea and uric acid or even CO2. Larger organisms such as fish are well known to produce ammonia which is exchanged through the gills.  Microorganisms and their various proteins, fall to the bottom of the ocean as they die. Permanently sequestering some of the CO2 in various proteins and tissues.

Two recent papers were published on OA and the change of pH.  The most recent published paper from December found

“[the] observed annual variability (~0.3 units) and diurnal variability (~0.1 units) in coastal ocean acidity are both similar in magnitude to long-term global ocean projections (~0.2 units) associated with increasing atmospheric CO”1.

This corresponds well with a paper published in 2011 from Scripps that found that even in the generally stable open ocean where pH tracks well with the CO2 hypothesis

“Our observations confirm an annual mean variability in pH at CCE-1 of nearly 0.1, suggest an inter-annual variability of ~0.02 pH, and capture episodic change” and even went further in their abstract stating “The effect of Ocean Acidification (OA) on marine biota is quasi-predictable at best”2.

A third paper Found much the same

“It is important to place these [OA] changes within the context of pH in the present-day ocean, which is not constant; it varies systematically with season, depth and along productivity gradients. Yet this natural variability in pH has rarely been considered in assessments of the effect of ocean acidification on marine microbes.”3

And my personal favorite quote:

“Therefore, an appropriate null hypothesis may be, until evidence is obtained to the contrary, that major biogeochemical processes in the oceans other than calcification will not be fundamentally different under future higher CO2/lower pH conditions“3

Thus while the model depicting OA as a function of CO2 may be relatively accurate, in some sites the interannual variability exceeds predicted changes and most impact studies seem to neglect this. To be clear dramatic variability of the carbonate system endorses the OA theory and its purported negative impacts.

There is however one more issue with the OA hypothesis, and it stems from the same equilibrium equations used for its validation. Up until this point we have proceeded with the assumption that atmospheric CO2 concentration is causing the changes in hydrogen ion concentration. However natural biological, geological, and chemical sources induce a far greater change in hydrogen ion concentration or pH on inter-annual timescales. An increase in hydrogen ion concentration, assuming a large enough carbonate source, will produce an increased equilibrium value for atmospheric CO2.

Thus any factor which increases the mean of biological activity, will necessarily increase the mean of CO2 in the atmosphere. Any increase in mean CO2, through this mechanism, will result in a relative decrease of radiocarbon (C14) in the atmosphere due to the marine reservoir effect. A mean change in biological activity can be brought about through increases in total solar irradiance, global mean temperature increases, or other unknown factors

Not only is it almost impossible to determine the true effect of anthropogenic emissions on OA, it becomes very difficult to separate anthropogenic carbon sources from oceanic ones in regards to the isotopic concentration in the atmosphere. Without good data on this variance the calculations for global carbon balances may be biased. The same conclusion was found in this 2013 paper

“we detected a mean difference between the boundary layer and 5 m pCO2 of 13 ± 1 µatm. Temperature gradients accounted for only 11% of this pCO2 gradient in the top meters of the ocean; thus, pointing to a heterogeneous biological activity underneath the air-sea boundary layer as the main factor controlling the top meters pCO2 variability. Observations of pCO2 just beneath the air-sea boundary layer should be further investigated in order to estimate possible biases in calculating global air-sea CO2 fluxes.”4

This is not to say such factors invalidate the theory of OA or anthropogenic emissions, it simply means that they have not been investigated sufficiently to rule them out.

3. What about demonstrable harm?

One of the other criticisms found in the rebuttal related to my statements regarding demonstration of harm. Specifically I stated that if they want to claim there is some sort of harm imposed by OA they need to perform an experiment, and they hadn’t. In the rebuttal there is a list of experiments theoretically showing harm as the result of increased CO2.  I highly recommend reviewing them if you get a chance.

I clearly should have clarified my statement. It’s not that no experiment regarding CO2 and OA had been performed, I had already gone through the abstracts of most of his citations, I took issue with their validity.  I already addressed in the previous section inherent ecological variability, but there are far more problems with this series of studies than simple ecological variance.

First within a water column there is a pH variance and pH sensitive organisms such as Ophiothrix Fragilis choose to live within their pH optimum. From Dupont et al

During the period of May to September, the pH in gullmars fjord decreases with depth (ranging from 8.33 and 7.97), but never falls below 8.03 in the upper 30m where ophiothrix fragilis larvae are concentrated”

In this case they tested conditions at a pH of 8.1, 7.9 and 7.7 assuming a delta pH of -.2 and -.4. From their quote regarding the natural habitat of the species, again ignoring ecological variability, the lowest value they should have been testing is a pH of about 7.93.You cannot forcibly change the pH in a controlled system with a sensitive organism and claim significant results when the natural environment has variability that exceeds the control parameters for the experiment.

Secondly in almost all cases the studies evaluated the organisms over a very short time span, typically 6-8 weeks. This is not the same as evaluating a stable colony, nor is it akin to studying the adaptability of a species to a change in conditions. For calcifiers the ability to regulate pH at the site of calcification is important to their ability to calcify. The time to ramp up synthesis of required compounds to maintain a high pH at calcification sites may exceed the period of study.  While calcification rates may decrease this is not the same as shell dissolution as was alluded to in the NOAA video.

A study evaluating the ability of 18 different organisms to calcify under varying pCO2 conditions found that in 10 cases, when the solution was under saturated with aragonite calcification rates dropped. For 7 of the species calcification rates actually increased with moderate pCO2 and for 3 of the 7 they received the highest calcification rate at a pCO2 reflecting 2856ppm. The study concluded

“whatever the specific mechanisms involved, our results suggest that the impact of pCO2 on marine calcification is more varied than previously thought”6

Simply put you cannot take a system which neglects: temporal, generational, ecological and habitat based variables and apply those results, no matter how significant, to a system which does experience these effects. Like I mentioned before, there have been no studies performed which demonstrate harm from OA.

Furthermore this ignores the fact that calcifiers originally evolved under very high pCO2 >6000ppm conditions. In the rebuttal this point was conceded with a response that adaptation and evolution to such rapidly changing conditions is not possible.  While I could not find the referenced work. I would contend that it is factually incorrect. While the time necessary for the evolution of an entirely new species would likely exceed the period of time over which OA is going to occur, a response to the changing chemistry, which marine calcifiers already have to handle yearly variation is not unlikely.

It is certainly not unprecedented. The finches of the Galapagos have been shown to alter beak sizing as a response to drought or competition.

“From 1972 to 2001,Geospiza Fortis (medium ground finch) and Geospiza Scandens (cactus finch) changed several times in body size and two beak traits. Natural selection occurred frequently in both species and varied from unidirectional to oscillating, episodic to gradual. Hybridization occurred repeatedly though rarely, resulting in elevated phenotypic variances in G. Scandens and a change in beak shape.”7

We also learned of the effect of cars on a species of swallow in southwestern Nebraska, influencing the length of their wings in less than 30 years8. There is of course the incidence of the bacteria, discovered in 1975 evolving a unique enzyme to digest nylon, which wasn’t invented until 1935. There is even evidence of fish size, change and reproductive maturity varying as a result of our fishing regulations.

Frankly neither the pH range nor the time frame for OA seems to be outside natural variation. There is also ample evidence that more significant physiological changes can happen in shorter time frames. At the end of the day, before we get all hot and bothered by OA we need to sit back and acknowledge that the species in contention not only show a wider reaction range than is commonly presented, but that whatever their method for calcification is, they simply need to increase the metabolic rates, or the mean metabolic rate of the species through natural selection, to adapt to changing oceanic conditions.

4. Clearly There Must be Some Amazing Data Supporting the Hypothesis.

In the first essay I mentioned several points of contentions with the OA hypothesis. I have addressed my core mistakes and gone into the details and quibbles I have with the rebuttal. But there was one point I made in the original essay which was never touched on in the rebuttal. There is almost no data backing up the OA hypothesis.

As a refresher course on the history of pH; it was conceived of originally in 1909.  It was later revised in 1924 to accommodate measurement by electrochemical cells. It wasn’t until 1936 that the first commercial pH meters were available.  In the 1970’s the first portable pH meter was released. So if all of the major development in pH meters occurred in the 1900’s and the concept of pH wasn’t even thought up until 1909 how do we get the following graphic

image

From Wikipedia :Estimated change in sea water pH caused by human created CO2 between the 1700s and the 1990s, from the Global Ocean Data Analysis Project (GLODAP) and the World Ocean Atlas

An engineer showed me that graphic during a debate over the summer regarding CO2 and OA.  I love it, it’s a beautiful graphic, and it is entirely farcical. Luckily the tag on Wikipedia mentions that it is the estimated sea change. Unfortunately most people don’t understand the difference between a calculated value and a measured one as demonstrated by the first table on the Wikipedia page for ocean acidification. Note the field result stated next to pre-industrial levels, luckily this has been amended to reflect this is not in the citation given.

To really understand how strong of an argument there is for OA we have to look at the data. The very first worldwide composite of pH data for the oceans came from the GLODAP project. The goal was to establish a climatology for the world’s oceans.  This is not an easy endeavor and I do respect the attempt but the result is frankly untrustworthy.  While it did define an oceanic pH value in the 1990’s it did so with some gaping holes in its analysis.

Wikipedia describes some of the missing areas as the arctic ocean, the Caribbean sea, the Mediterranean sea and maritime southeast Asia.  However on their own website they state

“Anthropogenic CO2 was estimated for the Indian (Sabine et al. 1999), Pacific (Sabine et al. 2002), and Atlantic (Lee et al. 2003) basins individually as the data were synthesized.”

More specifically the entire purpose of the analysis was to estimate the amount of stored anthropogenic carbon. They estimate the uncertainty on this value to be 16% of the total inventory.

With a large part of the ocean completely unsampled, and certainly lacking regular pH measurement effort, what other data is available then? The short answer is none. Unfortunately pH measurements and instrumentation require constant calibration which is not easily performed in long autonomous measurements.  The 2009 document from the scientific committee on oceanic research states

“If one is to get a detailed picture of ocean acid base chemistry, they need to be measured precisely with a low uncertainty, but to date such low uncertainties have not been demonstrated for oceanic pH measurements”9

The core of my skepticism in AGW and more specifically the catastrophic elements is always questionable data. This is no different for ocean acidification and the purported claims.

5. Conclusions

After finishing my research and corrections, I was certainly able to corroborate the numerical consensus regarding pH changes as a function of CO2 concentration.  However the correction did little to curb my skepticism of an anthropogenic ocean acidification hypothesis and the purported harms. There are simply too many false assumptions required for the idea to play out through its mathematical model.

The same problems arise between small and large ballistics modeling.  For lower speeds and shorter distances it is easy to neglect air resistance and get an approximate answer. But for longer distances or higher velocities we end up having to take into account air resistance. The current approach to modeling OA and organism adaptability is akin to trying to understand flight while neglecting lift and concluding it is impossible.

There is direct contrarian evidence to the idea that marine pH is dependent on CO2. pH changes regularly in the ocean, to a greater magnitude than the anticipated effect of CO2 and in a shorter period of time. The ability of an organism to adapt to changing conditions is a huge variable between species, and the ability to adapt over a period of time has not been studied.

Beyond these factors there simply has not been a solid organized long term study of oceanic pH to validate any of the claims. As is frequent in climate science we see gorgeous model visualizations rather than actual data, and we see claims rather than facts.

Outside of these significant factors there is another aspect of OA which frankly needs more research. The fact that pH changes in response to biological activity, begs the question whether humankind is fully to blame for the increase in atmospheric CO2. Any factor that increases the activity of marine life, must necessarily increase the rate of flux of marine CO2 into the atmosphere.

References

1. “Dramatic Variability of the Carbonate System at a Temperate Coastal Ocean Site (Beaufort, North Carolina) is Regulated by Physical and Biogeochemical Processes on Multiple Timescales,” by Zackary I. Johnson, Benjamin J. Wheeler, Sara K. Blinebry, Christina M. Carlson, Christopher S. Ward, Dana E. Hunt. PLOS ONE, Dec. 17, 2013. DOI:10.1371/journal.pone.0085117

2.Hofmann GE, Smith JE, Johnson KS, Send U, Levin LA, et al. (2011) High-Frequency Dynamics of Ocean pH: A Multi-Ecosystem Comparison. PLoS ONE 6(12): e28983. doi:10.1371/journal.pone.0028983

3. Joint, Ian, Scott C. Doney, and David M. Karl. “Will Ocean Acidification Affect Marine Microbes?” The ISME Journal (2010): n. pag. Print.

4. Calleja, Maria Ll., Carlos M. Duarte, Marta Álvarez, Raquel Vaquer-Sunyer, Susana Agustí, and Gerhard J. Hernd. “Prevalence of Strong Vertical CO2 and O2 Variability in the Top Meters of the Ocean.” Global Biogeochemical Cycles 27.3 (2013): 941-49. Print.

5. Dupont, S., J. Havenhand, W. Thorndyke, L. Peck, and M. Thorndyke. “Near-future Level of CO2-driven Ocean Acidification Radically Affects Larval Survival and Development in the Brittlestar Ophiothrix Fragilis.” Marine Ecology Progress Series 373 (2008): 285-94. Print.

6. Ries, J. B., A. L. Cohen, and D. C. McCorkle. “Marine Calcifiers Exhibit Mixed Responses to CO2-induced Ocean Acidification.” Geology 37.12 (2009): 1131-134. Print.

7.Grant, Peter R., and Rosemary Grant. “Unpredictable Evolution in a 30-Year Study of Darwin’s Finches.” Science 296.5568 (2002): 707-11. Print.

8. Brown, Charles R., and Mary B. Brown. “Where Has All The Roadkill Gone.” Current Biology 23.6 (2013): 233-34. Print.

9.  Report of Ocean Acidification and Oxygen Working Group. Scientific Committee on Oceanic Research, 2009. Web. 24 Jan. 2014. http://www.scor-int.org/OBO2009/A&O_Report.pdf

About these ads

116 thoughts on “Ocean Acidification Expansion

  1. If I am reading this properly, the 2.3ppm that man is assumed to be placing into the atmosphere yearly could very easily be all Ocean processes because we have not defined them well enough or studied them to know. In short; We do not know. That said, the indicators show there is sufficient data to implicate other sources than man.

    Once again the failure of the CAGW crowd to rule out other possible sources is exposed. yYet they want to smash our economies and put us back in caves to “save the planet”…

    Very well done! This leaves me pretty much speechless.

  2. It is certainly not unprecedented. The finches of the Galapagos have been shown to alter beak sizing as a response to drought or competition.
    =========
    a great many species are known to have genes that turn on or off between generations depending on environmental conditions. In effect a single species acts as multiple species, depending on conditions. we have only scratched the surface into research in this area.

    few if any species have a reproductive cycle that is longer than what is suggested for the maximum worst case speed of climate change. thus, any study of the effects of OA would by necessity require that the study consider multiple generations, as well as great difficulty in keeping marine organisms alive in artificial environments.

  3. I read that in the Bering sea in tests the Ph varied from a surface 8.2 to 7.8 at a depth of 20 metres, how on earth do you begin to measure the ph of the seas as it is constantly changing up and down especially around coastlines.

    The tests in the lab to simulate the seas becoming less base are suspicious using Sulphuric! and Nitric acid! and with no buffering mechanism.

  4. Steve,
    Thank you for this excellent summary. Too often, the short-hand talking points become the accepted “consensus”. Ocean acidification is one more of the terms the CAGW believers accept as dogma. We need more authors to educate about the science of the earth’s climate, rather than zealots preaching the gospel of blind faith. Thank you.

  5. but the synopsis is there is no real way to determine if the increase in atmospheric CO2 is mostly anthropogenic. The same equilibrium relationship that drives the doom and gloom predictions of rising atmospheric CO2, works in reverse if the pH drops below the atmospheric equilibrium value.

    This may be one of the strongest arguments against an industrial impact on atmospheric CO2 and for natural forces affecting atmospheric CO2.

    Putting my decidedly antique ex-Biology major hat back on (I’ve spent the past thirty-mumble years as a physician), permit me to observe:

    Oh. My. [Copulating]. Ghod.

    Has anybody gotten on the Ouija board USB interface and communicated this to Charlie Keeling yet?

  6. A substantial amount of the official alarm comes from PMEL, where astoundingly bad papers have been published on the linkage between ocean pH and Pacific oyster reproductive success at the Netarts Bay hatchery, completely overlooking the natural estuarine pH seasonal variation that Netarts Bay does not have. Seem my post last year, Shell Games, over at Climate Etc. for details.
    You are spot on that natural pH variation in almost all marine ecologies exceeds the maximum 0.2 pH change under RCP6.0 now foreseen by AR5 once buffering is taken into account, which AR4 incorrectly did not do.

  7. “I mentioned the EPA value for change on ocean temperature as 1.5-1.75 C when in fact it was Fahrenheit. I assumed that all reputable agencies worked with SI units but I was wrong. ”

    You were not wrong. The EPA is not reputable.

  8. While I am very much opposed to the CAGW movement, let’s not mix in weak arguments, as that is unnecessary.

    The findings are contained in the second section of the essay, but the synopsis is there is no real way to determine if the increase in atmospheric CO2 is mostly anthropogenic.

    The mass of Earth’s atmosphere is about 5150 trillion metric tons (easily verified / googled). Total CO2 in the atmosphere at one time is presently about 400 parts per million by volume. Since CO2 has a molecular weight of 44.01 g/mol whereas the mean molecular weight of air is around 28.97 g/mol, that means CO2 is about 608 parts per million of the atmosphere by mass.

    Thus total CO2 in the atmosphere right now is around 3.13 trillion metric tons, when it is around 400 ppm per volume.

    Over an example 5 year period from 2008 to 2013, measured CO2 in the atmosphere increased by 10.89 ppm by volume. Having done the preceding calculations, it is trivial to
    multiply out (10.89 / 400) * 3.13 trillion metric tons, to so determine that corresponded to a rise in CO2 in the atmosphere of about 85.2 billion metric tons over a 5 year
    period.

    So CO2 in Earth’s atmosphere has been measured to go up recently by around 17 billion metric tons a year.

    That figure stands out in its magnitude, because, for example, 9.7 billion metric tons of carbon was effectively combusted in 2012 from human fossil fuel burning and cement production. (Such being around that number isn’t in much dispute; just google fossil fuel combustion GtC, although it’d be implied by even general economic data like usage figures for coal, natural gas, and so on). Since carbon has a molecular weight of 12.01 g/mol, whereas CO2 has a molecular weight of 44.01 g/mol, those 9.7 gigatons of carbon became, upon oxidation, 35.5 billion metric tons of CO2.

    So, as stands about the preceding, civilization emits enough CO2 to be about double the measured rise of it in the atmosphere.

    Some increase in atmospheric CO2 has come from warming of oceans, but, if you look at the plots of temperature driven CO2 release in ice age cycles, it involved less change of atmospheric CO2 in ppm at the same time as much greater change in temperature, compared to the past century. So most of the net increase in CO2 being manmade is quantitatively reasonable and is the case.

    The preceding is despite the fact that total circulation of CO2 by the biosphere per year dwarfs the human addition: The former is mainly merely going in a loop. (As an analogy, if there is a water container with a pump constantly pumping in at X rate while pumping out at about the same X rate, its water level will stay near constant, while adding Y more rate of unbalanced water input will cause a substantial net increase over time even if Y is far less than X).

    Fortunately, however, the manmade increase in CO2 is not harmful but rather beneficial. A portion of the CO2 emissions not ending up in the oceans, as well as some of the CO2 which does, has gone into increased biomass. For instance, CO2 in the atmosphere doubling relative to pre-industrial times would correspond to tens of percent increase in the average growth rates of terrestrial plants (except when limited by other factors like insufficient fertilizer usage), plus huge increase in water usage efficiency for them due to not as much stomatal conductance (essentially pore opening) needed to get enough CO2 (so less evaporative water losses from leaf surfaces), while aquatic plants benefit too.

    The biological benefits of CO2 increase are extensively discussed and demonstrated at http://nipccreport.org/ (the very opposite of the IPCC’s brief misleading treatment)

    As for ocean “acidification” (tiny pH change and still further from acid than neutral water), the lack of such being the hyped about problem is illustrated under the various links at http://www.nipccreport.org/archive/aquatic.html

    As for the temperature effect of CO2 in regard to it not being the prime climate driver, such is illustrated in my usual grand image presentation showing what actually caused past climate variations from the LIA to the current “pause” in global warming: http://tinyurl.com/nbnh7hq

    Furthermore this ignores the fact that calcifiers originally evolved under very high pCO2 >6000ppm conditions.

    Good point and very relevant. For conciseness, I focused on a part of your article where I disagreed with its presentation, but of course there are other parts making very valid points.

  9. The tests in the lab to simulate the seas becoming less base are suspicious using Sulphuric! and Nitric acid!
    ============
    Adding acid to sea water to simulate CO2 is nonsense. the simplest way to demonstrate this is to go to your hardware store and buy a gallon of muriatic acid (mostly hydrochloric acid). It usually only costs a couple of dollars and is used routinely for cleaning cement, pools, etc.

    Now take your gallon of muriatic acid and pour it into the container of sea water – if you dare. The cloud of yellow gas you will release is chlorine. extremely toxic and corrosive to the lungs. yet we routinely hear of so called scientists using hydrochloric acid to simulate CO2.

    If the result you want to demonstrate is toxicity, adding acid to sea-water is the sure way to ensure the result you are seeking.

  10. Several recent marine biology papers look for effects of “acidification” at CO2 seeps, where CO2 bubbles up from volcanic vents. Is it possible that any measured acidification is dominated by sulfur that is also bubbling up at these vents?

  11. Steven, a person can change the pH in a lab, aquarium, etc by adding an acid long enough to deplete the buffer…fish aquarium people run into that all the time, and the solution is just add more buffer. A closed house in winter can have CO2 levels over 1000 ppm.

    The oceans can not become “acid” until they run out of buffer..
    ..calculate the buffer pool in the oceans is the way to go

    You’ll find that the oceans will never run out of buffer……..

  12. If increased pH is really harmful it may be the only harmful aspect of increasing atmospheric carbon dioxide. I personally doubt it. Ask yourself: is it possible that after spending zillions of dollars examining all aspects of carbon dioxide in the atmosphere, pH change is the only bad thing they can come up with? That greenhouse warming scare of theirs is entirely a bust because Hansen did not detect the greenhouse effect in 1988 but they still keep yapping about it.. That is because Hansen included the early century warming from 1910 to 1940 as part of his “hundred tear warming” curve that was supposed to prove that the greenhouse effect exists. Under no circumstances can this warming be called greenhouse warming because there was no increase of atmospheric carbon dioxide in 1910 and carbon dioxide was not removed from the air in 1940. This lops off 60 years from his 100 year proof. What is left of this 100 year warming curve is now a see-saw: 25 years of cooling followed by 23 years of warming. Not something to build the existence of an international organization upon as was done after his talk to the Senate.

  13. Like most postings here I learned a lot. However, the bit of me that claims “editor” says that this paper should have been gone through to clarify some items and to correct some spelling and grammatical errors. I don’t want to come across as a naysayer here, for there is so much valuable information in this paper, but in places it could have been more hard-hitting.

    Ian M

  14. “Furthermore this ignores the fact that calcifiers originally evolved under very high pCO2 >6000ppm conditions.”
    ========
    as short as 4 million years ago the oceans were more acid (less caustic) than they are today. if anything, the current ice age oceans are a problem for sea life, because of the ability of caustic solutions to dissolve fat/hair. marine animals routinely excrete mucous and similar substances to protect themselves from today’s oceans. If anything, reducing the pH by adding CO2 would make the oceans less caustic for marine life, reducing the need to excrete protective slime. Thus it is hard to see how increasing CO2 would be necessarily harmful.

  15. You are spot on that natural pH variation in almost all marine ecologies exceeds the maximum 0.2 pH change under RCP6.0 now foreseen by AR5 once buffering is taken into account, which AR4 incorrectly did not do.
    =========
    apparently climate science skipped inorganic chemistry. the “salt” in salt water is a buffer. to change salt water to an acid is simple, you need only first remove the 11 billions cubic miles salt in the oceans.

  16. Henry, CO2 rise in the atmosphere is not linear. It goes up and it goes down with a net change in the area of 2ppm by volume annually. So there is more to CO2 in the air than just burning CO2. insects for instance put out more CO2 than we do, so the relative size of what we burn and its final destination in chemical form is tiny compared to what is given off and taken in by other parts of the biosphere and environment. So really this area of science needs a lot more study before you can point to something as being the main driver.
    v/r
    David J. Riser

  17. David Riser says:
    April 27, 2014 at 7:56 am
    Henry, CO2 rise in the atmosphere is not linear. It goes up and it goes down with a net change in the area of 2ppm by volume annually. So there is more to CO2 in the air than just burning CO2. insects for instance put out more CO2 than we do, so the relative size of what we burn and its final destination in chemical form is tiny compared to what is given off and taken in by other parts of the biosphere and environment.

    If you read all of my 7:24am post, the ratio of annual biosphere CO2 cycling to annual human emissions is noted and addressed in a paragraph several down.

  18. P.S.

    In my original post, I forgot to mention one additional indication (though read that comment first to put in context): measured change in the C-13 to C-12 ratio of carbon in atmospheric CO2, since that isotope ratio is low in fossil fuels, providing a relative signature

    However, if not for the anti-human bias of most hardcore environmentalists, observations on the increase in atmospheric CO2 over the past century being primarily manmade would be more often in the style of Dr. Idso’s presentation on its observed benefits: CO2 and the Biosphere: The Incredible Legacy of the Industrial Revolution. A brief summary is at http://climate.umn.edu/doc/journal/kuehnast_lecture/lecture3.pdf , although such is a lengthier book (e.g. seen at https://www.google.com/search?q=biosphere+incredible+legacy+of+the+industrial+revolution )

  19. Henry,
    While you skirt the issue, my point is that its a bit early in the understanding to say that it is reasonable to assume that CO2 in the atmosphere is driven by burning fossil fuels. That is all I was trying to say. We still don’t know enough. Time to head to the ocean and fields and do some measuring for enough time to know who the players are and what their relative output is.
    v/r,
    David Riser

  20. Henry Clark says:
    April 27, 2014 at 8:03 am
    measured change in the C-13 to C-12 ratio of carbon in atmospheric CO2, since that isotope ratio is low in fossil fuels, providing a relative signature
    ===========
    Spencer Part2: More CO2 Peculiarities – The C13/C12 Isotope Ratio

    BOTTOM LINE: If the C13/C12 relationship during NATURAL inter-annual variability is the same as that found for the trends, how can people claim that the trend signal is MANMADE??

    http://wattsupwiththat.com/2008/01/28/spencer-pt2-more-co2-peculiarities-the-c13c12-isotope-ratio/

  21. I wonder how they acidified it and lakes already have a lower pH.

    “During the acid rain issues in the 1980s, a lake basin in Wisconsin was deliberately acidified
    (with EPA and NSF funding) to a pH of 4.7 then allowed to recover. “Some species were
    decimated and others thrived, but the sum-total of life in the lake stayed the same.” This is a
    level of acidification 1,000 X the worst-case scenario for the oceans”

  22. “Thus any factor which increases the mean of biological activity, will necessarily increase the mean of CO2 in the atmosphere. Any increase in mean CO2, through this mechanism, will result in a relative decrease of radiocarbon (C14) in the atmosphere due to the marine reservoir effect. A mean change in biological activity can be brought about through increases in total solar irradiance, global mean temperature increases, or other unknown factors
    Not only is it almost impossible to determine the true effect of anthropogenic emissions on OA, it becomes very difficult to separate anthropogenic carbon sources from oceanic ones in regards to the isotopic concentration in the atmosphere.”

    I and others have been making just that point in relation to the isotope ratio aspect for some time.

    It also seems to support the views of Murry Salby.

    Any comment from Ferdinand Engelbeen ?

    He has been a prolific supporter here of the isotope ratio diagnosis for anthropogenic influence on atmospheric CO2.

  23. CO2 levels were much higher back in the age of dinosaurs. Why didn’t the sea life back then die of ocean acidification?

  24. Steven, if you have not please check out this NIPCC report.
    http://www.nipccreport.org/reports/ccr2b/pdf/Chapter-6-Aquatic-Life.pdf It s a very long and detailed well referenced report.
    Of particular interest to you, and well supporting your research s this section…
    6.3 Ocean “Acidification”
    6.3.1 Introduction
    6.3.2 Effects on Marine Plants
    6.3.3 Effects on Marine Animals

    This is one small section, (200 plus pages fully documented.) of a much larger report.
    BTW Mr. Mosher, perhaps you should read this. It may begin to answer some questions you had on another post.

  25. but the synopsis is there is no real way to determine if the increase in atmospheric CO2 is mostly anthropogenic

    I can tell you at least one thing. All of the CO2 that has been emitted by the millions of air plane trips over the last 100 years has not gone into the deep ocean.
    As well, the following three people with doctors degrees agree that man is responsible for most of the increase in CO2.

    Dr. Spencer:

    http://www.drroyspencer.com/2014/04/skeptical-arguments-that-dont-hold-water/

    “7. WARMING CAUSES CO2 TO RISE, NOT THE OTHER WAY AROUND The rate of rise in atmospheric CO2 is currently 2 ppm/yr, a rate which is 100 times as fast as any time in the 300,000 year Vostok ice core record. And we know our consumption of fossil fuels is emitting CO2 200 times as fast! So, where is the 100x as fast rise in today’s temperature causing this CO2 rise? C’mon people, think. But not to worry…CO2 is the elixir of life…let’s embrace more of it!”

    Dr. Latour did not agree with much of what Dr. Spencer wrote, but he did agree here:

    http://www.drroyspencer.com/2014/04/skeptical-arguments-that-dont-hold-water/#comment-111993

    Pierre R Latour says:
    April 26, 2014 at 3:28 PM
    “7. Your assertion fossil fuel combustion adds CO2 to atmosphere is correct.”

    Dr. Lindzen

    http://i.telegraph.co.uk/multimedia/archive/02148/RSL-HouseOfCommons_2148505a.pdf

    page 18
    “On the matter of global climate change, APS notes that virtually all
    reputable scientists agree with the following observations:
    Carbon dioxide is increasing in the atmosphere due to human activity;
    Carbon dioxide is an excellent infrared absorber, and therefore, its
    increasing presence in the atmosphere contributes to global warming;

    The first two items refer to the trivial agreement.”

    However that does not address the big issue. Again quoting from Dr. Lindzen:
    “It is not about whether CO2 is increasing: it clearly is. It is not about whether the increase in CO2, by itself, will lead to some warming: it should. The debate is simply over the matter of how much warming the increase in CO2 can lead to, and the connection of such warming to the innumerable claimed catastrophes. The evidence is that the increase in CO2 will lead to very little warming, and that the connection of this minimal warming (or even significant warming) to the purported catastrophes is also minimal.”

  26. NIce article Steve. but I think you forgot one big elephant in the data. H2CO3 + CaCO3 -> 2HCO3.
    There are gigatons of carbonate sources in the oceans, the oceans buffer. Thus the statement
    “For example if I doubled the concentration of hydrogen ions, the concentration of carbonate ions will necessarily drop by half to maintain the equilibrium.” Is not correct!. You get even more HCO3 in the ocean when you add CO2 than you calculate due to increased dissolution of CaCO3. Therfore the CO3 doesn NOT drop to half when you double H+. It does in a sterile flask with NO CaCO3 buffer sources, but the ocean is different.
    Q: In the lab, how does one dissolve CaCO3 into solution which has very low solubility in pure water?
    A: Bubble in CO2!
    And when you do this, total CO3 ion concentration does not decrease, it increases.

  27. ferdberple says:
    April 27, 2014 at 7:30 am
    Now take your gallon of muriatic acid and pour it into the container of sea water – if you dare. The cloud of yellow gas you will release is chlorine.

    I strongly doubt that, Fred. If there was anything already in seawater to oxidise significant amounts of chloride ions to chlorine then it would already have done so because of the salt present. It would also have first oxidised the organic compounds and inorganic ions such as bromide to bromine. You might get tiny amounts formed due to photochemical oxidation (UV sunlight and oxygen, ozone), but not “clouds of yellow gas.”

  28. When people say that some component of the atmosphere is 400 ppm…..” by volume”…..just how do they separately measure the volume of that component and the volume of the rest of the sample ??

    Given that the volume of the atmosphere is not fixed, and the Temperature and pressure also depend on where the sample was collected, I can’t see what earthly use, such a measure is.

    How long has it been, since it was proven, that matter comes in atoms and molecules; each with a fixed amount of material, mass, size, and properties?

    So why do they not simply count the molecules or atoms of each species in the sample and be done with it.

    When somebody tells me that CO2 is present in the atmosphere at 400 ppm; that to me means that one in every 2500 molecules in a sample of atmosphere is a CO2 molecule.

    Any other measure is poppycock.

    CO2 absorbs LWIR radiation, by having A LONE MOLECULE of CO2 absorb A PHOTON of EM radiation, in some small spectral range near 15 microns (or other bands); and that one molecule of CO2 is not even cognizant that another molecule identical to it, even exists. It cares not how much volume it is in, whether 1 cc, or 1 liter, or 1 cubic km. It does care about its immediate neighborhood, as far as how close it is to other species, and how often and how fast, it gets to bang into something else, which are manifested in pressure and Temperature, but it is unaware of how much volume the atmosphere occupies; it is on its own, when it comes to grabbing a photon of EM radiant energy.

  29. Excellent article – it’s a shame that in each case, one person has to make an incredible contribution of labor and thought just to prove, once again, the *every* area of climate alarmism is, at its core, nothing but political BS piled on top of unsubstantiated claims based on wishful thinking, not evidence.

  30. ” There are no preindustrial pH measurements (more on this later). Without pre-industrial pH or for that matter any one of the other chemical species we cannot easily determine the equilibrium concentrations of any of the ions.”

    More simply put: what is the “optimum value” and are we moving towards it or away from it due to factors that we can control as compared to factors we can’t.

    Climate alarmists assume we are moving away from optimum and that we can change the things that humans are doing in a manner that mitigates any damage we are doing. Apart from zero interest by climate alarmists in finding the optimum, all the models I have seen have grossly overestimated the effect of human causes CO2, and thus show their authors have so far failed to accurately model a complex system even as they insist we must act.

    Indeed, while the climate models never seem to converge back to post hoc reality, the prescriptions of alarmists far more reliably converge on a few common socialist factors: bigger government, less liberty, less personal prosperity, fewer choices. This gives the appearance of an agenda more than a line of research.

  31. “””””…..Dr. Lindzen

    http://i.telegraph.co.uk/multimedia/archive/02148/RSL-HouseOfCommons_2148505a.pdf

    page 18
    “On the matter of global climate change, APS notes that virtually all
    reputable scientists agree with the following observations:
    Carbon dioxide is increasing in the atmosphere due to human activity;
    Carbon dioxide is an excellent infrared absorber, and therefore, its
    increasing presence in the atmosphere contributes to global warming; …..”””””

    I consider myself a scientist having made my living doing science for more than 55 years; and I’m also reputable; having never been arrested for any scientific malfeasance; or other kind.

    And I’m a fan of Dr. lindzen but I would never say what the good professor has said in that quote.

    No I’m not wildly in disagreement; I just want to change one single word.

    For “global” warming, read “atmospheric” warming.

    I have no idea how the atmosphere might “warm” the globe, but it might.

    Certainly not by conductive or convective “heat” transfer; because the second law of thermodynamics prohibits that (free net flow of heat from cold to hot).

    And the operation of feedback processes due to water vapor and clouds, would seem to interfere with EM radiative warming of the surface, by the atmosphere.

    Other than that I agree with Lindzen’s conclusion; is it (if it is), enough to worry about ??

    Not for me !!

  32. Stephen Wilde says:
    April 27, 2014 at 8:35 am

    Any comment from Ferdinand Engelbeen ?

    Here we come…

    First, an essential point:
    All reactions in the oceans are equilibrium reactions. If one of the concentrations change, all other concentrations will change too. In the case of more CO2 in the atmosphere, that gives an increase of CO2 in the surface waters en hence more total dissolved inorganic carbon (DIC = CO2 + bicarbonate + carbonate) in the ocean surface layers plus some more H+ ions, which makes that the pH slightly lowers.
    If the opposite happens: for some reason the pH lowers, then the equilibrium reactions are pushed from carbonate to bicarbonate and from bicarbonate to CO2. Thus pushing more CO2 into the atmosphere. But that also means that the total inorganic carbon (DIC) in the ocean top layer will DEcrease.
    The same for increased biolife: an increase in biolife will reduce DIC, as part of the planktonic shells, fish releases,… will sink out of the surface layer at the cost of CO2 and its derivatives in the ocean waters.

    Thus it is quite easy to detect what the direction of the CO2 flux is: if it is out of the oceans by pH or biolife, DIC will decrease over time. If it is CO2 out of the atmosphere entering the oceans, DIC will increase over time with decreasing pH. We have a lot of sporadic measurements of DIC over time, but fortunately also a few longer-term series, representing most of the NH Atlantic and Pacific oceans:
    http://www.biogeosciences.net/9/2509/2012/bg-9-2509-2012.pdf Fig 5. of the 18-year Bermuda series and
    http://www.pnas.org/content/106/30/12235.full.pdf Fig.1 for the Hawaii series. The latter doesn’t show DIC, but as the mean pCO2 of the atmosphere is above the pCO2 of the ocean surface, the flux is from atmosphere into the oceans.

    That is the also case for the “average” difference in pCO2 between atmosphere and oceans all over the world. See:
    http://www.pmel.noaa.gov/pubs/outstand/feel2331/exchange.shtml and following pages.

    Then the 13C/12C ratio: the δ13C level of the atmosphere pre-Industrial was -6.4 per mil. Sinds the Industrial revolution that dropped to -8 per mil in lockstep with human emissions. The δ13C level of the deep oceans is between 0-1 per mil, while the surface is between 1-5 per mil. The difference is from the biological pump which increases the δ13C of the surface by dropping out low-13C organics into the deep waters. Thus any important release of oceanic CO2 would INcrease the δ13C level of the atmosphere, while we see a steady decrease as well as in the atmosphere as in the ocean surface waters. See:

    Last but not least, humans currently emit twice the amount of CO2 as measured as increase in the atmosphere. The uptake by the biosphere is known (about 1 GtC/year), based on the oxygen balance. Almost all of the difference (some 3.5 GtC/year) goes into the oceans, because all other known sinks are either much smaller or much slower.

    Thus sorry, the oceans as cause of the CO2 increase in the atmosphere is simply out of reality…

  33. Apparently I don’t need no stinkin calculations for ballistics. I seem instead to have an instinct for the trajectory of a .22 bullet coming from a 40 grain cartridge out to 300 yds. 10 for 10. And at 400? 4 out of 10. With nothing but a $25 dollar scope on a used Marlin .22 rifle. Not bad for aiming at nothing but a spot in the sky with the target somewhere below my visual picture. Don’t ask me how I do it. I have no idea. Other than I find the target, barely visible in my scope, then raise the gun for elevation instinctively. And fire. Moments later the microphone sends back a ping.

  34. I forgot to add, that I don’t fully grasp the full significance of Steven’s essay (IANAC), but I appreciate the effort he put into it.

    And I’m not the least bit worried about CO2 dissolving in the ocean. What are the white cliffs of Dover made out of ?? We’ve got the same stuff in Santa Cruz County.

  35. Some people assert that ‘ocean acidification’ is happening so fast that crustaceans are doomed. I only find this in fish tanks which are pumped to the high heavens over short periods of time to see the results. That is unrealistic and we are talking about 86 years to 2100.

    Here is a crustacean – less than 30 years.

    Abstract
    Dormant eggs record rapid evolution
    Nature 401:446. 1999
    Natural selection can lead to rapid changes in organisms, which can in turn influence ecosystem processes. A key factor in the functioning of lake ecosystems is the rate at which primary producers are eaten, and major consumers, such as the zooplankton Daphnia, can be subject to strong selection pressures when phytoplankton assemblages change. Lake Constance in central Europe experienced a period of eutrophication (the biological effects of an input of plant nutrients) during the 1960s-70s, which caused an increase in the abundance of nutritionally poor or even toxic cyanobacteria. By hatching long-dormant eggs of Daphnia galeata found in lake sediments, we show that the mean resistance of Daphnia genotypes to dietary cyanobacteria increased significantly during this eutrophication. This rapid evolution of resistance has implications for the ways that ecosystems respond to nutrient enrichment through the impact of grazers on primary production.
    Hairston, N.G., Jr., W. Lampert, C.E. Cáceres, C.L. Holtmeier, L.J. Weider, U. Gaedke, J.M. Fischer, J.A. Fox, D.M. Post.

    http://www.nceas.ucsb.edu/~post/abstracts.html

    Plus.

    Abstract – 2000
    Rapid Evolution of Reproductive Isolation in the Wild: Evidence from Introduced Salmon
    Colonization of new environments should promote rapid speciation as a by-product of adaptation to divergent selective regimes. Although this process of ecological speciation is known to have occurred over millennia or centuries, nothing is known about how quickly reproductive isolation actually evolves when new environments are first colonized. Using DNA microsatellites, population-specific natural tags, and phenotypic variation, we tested for reproductive isolation between two adjacent salmon populations of a common ancestry that colonized divergent reproductive environments (a river and a lake beach). We found evidence for the evolution of reproductive isolation after fewer than 13 generations.

    http://www.sciencemag.org/content/290/5491/516.short

    —————-

    Abstract – 2003
    Rapid Evolution of Egg Size in Captive Salmon

    http://www.sciencemag.org/content/299/5613/1738.short

  36. You were going down a fruitful path with biological responses, and then you left it. People forget about biology, and that’s often where chemists and physicists go awry when they deal with processes on Earth. All too often they incorrectly avoid “soft” sciences. Nitrogen fixation by cyanobacteria increases alkalinity in the ocean and other bodies of water. Have a look here

    http://www.princeton.edu/sigman/publications/pdf/KarlBiogeochemistry2002.pdf

    and the reference within that document here
    Moore B, Whitley E & Webster TA (1921) Studies of photo-synthesis in marine algae –
    1. Fixation of carbon and nitrogen from inorganic sources in sea water. 2. Increase of
    alkalinity of sea water as a measure of photo-synthesis. Proc. Roy. Soc. Lond. B 92: 51–58

    If there is an abundance of carbon, nitrogen, and phosphorous, a wide variety of photosynthetic organisms will flourish. However, when nutrients are limiting, often a limited number of species or one will dominate when those species have an ability to acquire the limiting nutrient. They may dominate when they have a clear survival advantage over the others. Cyanobacteria can be recognized in lakes as light green mats of algae floating on or near the surface. They appear when N is limiting, because they can fix nitrogen.

    Bodies of water at high elevation often have low alkalinity (depending on geology), but as it passes through and over various rock and soil formations, and into more biologically active areas, the alkalinity increases. It is not uncommon for high elevation mountain lakes to have pH in the high 5 to low 6 range. But of course, here the alkalinity is very low, because it never had a chance to develop. The relatively low pH values are not due to acid rain. At lower elevation, the alkalinity increases and water pH rises to a more common low 7 range.

  37. Demonstrating yet again the value of blog review of scientific papers, superior at least in the case of climatology to peer review by pals.

  38. David Riser says:
    April 27, 2014 at 8:13 am
    “Henry,
    While you skirt the issue, my point is that its a bit early in the understanding to say that it is reasonable to assume that CO2 in the atmosphere is driven by burning fossil fuels.

    What would it take to guess that the CO2 increase in the atmosphere over the 20th century was probably primarily unrelated to civilization’s CO2 emissions meanwhile?

    Among aspects:

    a) You’d have to guess that the CO2 emissions of civilization’s fossil fuel usage being of around the right magnitude for the measured net increase in atmospheric CO2 is probably just coincidental. If it was unconnected, it might be 10 or 100 times less, for instance, but that’s not what is seen.

    b) If believing modern CO2 change in the atmosphere was about all driven by warming (as it has to come from some cause, if not believing it from fossil fuel burning), you’d correspondingly expect and need CO2 history to match temperature history.

    Yet you couldn’t even possibly fully match CO2 to surface temperature, from how CO2 has gone up rapidly during global temperatures being flat (or rather actually declining) since 1998, to the actual history of temperatures as in http://hidethedecline.eu . You could try a little more with ocean heat content, but sea level change is a better indicator than CAGW-movement-source unverifiable OHC claims, while not having a pattern matching CO2 history.

    Admittedly, commonly shown CO2 reconstructions based on ice cores do seem to be wrong, so the debate can’t be conclusively concluded by just linking http://www.climate4you.com/images/GISP2%20TemperatureSince10700%20BP%20with%20CO2%20from%20EPICA%20DomeC.gif (which, if the official CO2 reconstruction wasn’t false, would be indirectly showing a small change of near 20 ppm CO2 occurring after slow ocean warming lagging the surface temperature variation).

    However, what would be more convincing for a present-CO2-is-predominately-just-due-to-temperature argument has not been shown:

    That would be CO2 reconstructions showing CO2 ppm to be higher than now’s 400 ppm every time when temperatures were higher than now.

    That includes in the Holocene Climate Optimum, for example, as there is no question whatsoever that the Holocene Climate Optimum definitely included long periods warmer than now (as implied by everything from proxy temperature reconstructions to fossilized arctic vegetation amounts, to higher sea levels back then).

    Then I’d have to look at the reconstruction and aim to evaluate it versus very contradictory other reconstructions, but it would be supportive evidence at least.

    Stomatal reconstructions do definitely exist which come relatively closer to the above than the ice core data. Ones coming close enough, though, throughout history, may be quite a different matter.

    David Riser says:
    April 27, 2014 at 8:13 am
    “That is all I was trying to say.”

    To prove that recent CO2 increase has been primarily manmade, to a degree of proof describable as utterly absolute, would take more effort than I’m willing to put out. I think arguing against the CO2 increase being primarily manmade is a weak argument and a distraction from how skeptics have much better ones, as well as not what an objective individual would guess as most probable (although, admittedly, there could indeed be more justifiable to investigate from a pure science perspective).

    But I don’t quite care enough about convincing people on that, so I probably won’t continue this debate much longer myself. The more important bigger picture (which we no doubt agree upon) is that CO2 is not the alarmist’s catastrophe anyway.

  39. Bullet proof stuff, Prof. Burnett. Maybe when you get a few spare minutes you could do some work on whether CO2 is actually a greenhouse gas. Or whether there is such a thing as a greenhouse gas. We have to gee back to basics and check the work of all these corrupt “climate scientists”

  40. Latitude says:
    April 27, 2014 at 8:15 am
    Spencer Part2: More CO2 Peculiarities – The C13/C12 Isotope Ratio

    BOTTOM LINE: If the C13/C12 relationship during NATURAL inter-annual variability is the same as that found for the trends, how can people claim that the trend signal is MANMADE??

    http://wattsupwiththat.com/2008/01/28/spencer-pt2-more-co2-peculiarities-the-c13c12-isotope-ratio/

    I’ll credit you for linking an interesting argument, although there is another side to it as seen in quite a series of comments by Ferdinand Engelbeen in that thread itself. Probably I’m not going to put in enough time on that matter to do it proper justice myself; most of my posting activity in most threads is otherwise directed.

    Still, aside from the C13/C12 ratio being only one part of this matter, the following is noteworthy:

    Observe that article was by Dr. Roy Spencer, published back in January 2008.

    Just 2 days ago, more recently, he published an article at http://www.drroyspencer.com/2014/04/skeptical-arguments-that-dont-hold-water/ which included him implying that the recent increase in CO2 is very much not just due to temperature increase. His specific choice of argument for that was suboptimal, since I suspect the ice core data doesn’t capture the full variation. Still, at least as of 2014, as the prior link implies, apparently Dr. Spencer himself believes that CO2 increase over the past century is not plausibly primarily just due to temperature increase.

    In aspects of (1) believing that CO2 increase over the past century was probably primarily human-caused and (2) meanwhile, though, being an utter opponent of the CAGW movement’s claims of catastrophe from it, I am in agreement with Dr. Spencer.

  41. Hoser says:
    April 27, 2014 at 10:22 am
    You were going down a fruitful path with biological responses, and then you left it. People forget about biology,
    ======
    Hoser, I agree 100%….

    Look a farming practices (fertilizer, irrigation, c4’s, etc), bacteria, etc…and you can find 100% of that c12

    chemistry is easy…biology is hard…..chemical biology is impossible

  42. PH can vary dramatically in just hours reaching levels expected for 2100. It’s that bad.

    Abstract – 2011
    Will ocean acidification affect marine microbes?
    ……….Useful comparisons can be made with microbes in other aquatic environments that readily accommodate very large and rapid pH change. For example, in many freshwater lakes, pH changes that are orders of magnitude greater than those projected for the twenty second century oceans can occur over periods of hours. Marine and freshwater assemblages have always experienced variable pH conditions. Therefore, an appropriate null hypothesis may be, until evidence is obtained to the contrary, that major biogeochemical processes in the oceans other than calcification will not be fundamentally different under future higher CO2/lower pH conditions.

    http://www.nature.com/ismej/journal/v5/n1/full/ismej201079a.html

    ———————–

    Abstract – December 19, 2011
    Gretchen E. Hofmann et al
    High-Frequency Dynamics of Ocean pH: A Multi-Ecosystem Comparison
    ………. These observations reveal a continuum of month-long pH variability with standard deviations from 0.004 to 0.277 and ranges spanning 0.024 to 1.430 pH units. The nature of the observed variability was also highly site-dependent, with characteristic diel, semi-diurnal, and stochastic patterns of varying amplitudes. These biome-specific pH signatures disclose current levels of exposure to both high and low dissolved CO2, often demonstrating that resident organisms are already experiencing pH regimes that are not predicted until 2100……..

    …..and (2) in some cases, seawater in these sites reaches extremes in pH, sometimes daily, that are often considered to only occur in open ocean systems well into the future [46]. …..
    DOI: 10.1371/journal.pone.0028983

    http://www.plosone.org/article/info%3Adoi%2F10.1371%2Fjournal.pone.0028983

  43. How about a nice little top-down model to look at our question.

    We have added ~150 BMTC to the ocean sink since 1850. That sink is ~38,000 BMTC, with ~2000 BMTC or so in the upper layer.

    That should allow us to calculate % of Hydrogen ions.

    We also have to consider that ocean acidification is said to have commenced around 1750, but it is not until two centuries later that CO2 is going to have any measurable impact. So that acidification until 1950 cannot have been CO2. Possibly drainage, dredging and dumping. Those factors would certainly apply now in some areas of the world.

  44. Henry Clark says:
    April 27, 2014 at 11:24 am

    I suppose that I have convinced Dr. Spencer that the increase of CO2 indeed is man-made…

    There is a longer reaction of mine on the work of Steven Burnett under moderation, but there is a long line of arguments that all show that humans are the source of the increase. See:

    http://www.ferdinand-engelbeen.be/klimaat/co2_measurements.html#The_mass_balance

    It needs some update, but as human emissions fit all observations and all alternatives I have heard of violate one or more observations, it is quite clear that humans are the cause.

    If that has much effect on temperature, that is the multi-billion dollar question which need real answers, not based on failed climate models…

  45. although there is another side to it as seen in quite a series of comments by Ferdinand Engelbeen
    =====
    And as Ferdinand “almost” argues….you can’t green the planet, increase farming, increase fertilizer, increase irrigation, increase tilling, etc….without have more vegetation decay.. .without also feeding the aerobic/anaerobic (anoxic) interface….without creating more habitat for denitrifying bacteria

    look at this and you’ll find all of your “missing” c12

  46. Thank you for this thorough look at the question.

    You say variation in Henry’s law coefficient is negligible over the temperature ranges involved. Citing EPA figures of global averages with heavy low-pass filtering.

    “Truthfully henry’s law constant corrections are not particularly necessary until you approach temperature variances of about 10C. ”

    Surely air-ocean are near instantaneous and looking at heavily filtered global averages really does not inform about the relevant range of the variables.

    ” Any factor that increases the activity of marine life, must necessarily increase the rate of flux of marine CO2 into the atmosphere.”

    Now there clearly is a component of d/dt(atm_CO2) that is directly proportional to SST.

    http://climategrog.wordpress.com/?attachment_id=720

    http://climategrog.wordpress.com/?attachment_id=719

    Can you reconcile those graphs with the explanation given in the article?

    regards, Greg.

  47. Ferdinand Engelbeen says:
    April 27, 2014 at 11:43 am
    “There is a longer reaction of mine on the work of Steven Burnett under moderation, but there is a long line of arguments that all show that humans are the source of the increase. See: http://www.ferdinand-engelbeen.be/klimaat/co2_measurements.html#The_mass_balance

    Ah, so you are still around as a poster, now as well as 6 years ago. Excellent.

    I see the 9:55am post of yours has appeared now and, like your link, is good reading.

  48. Ferdinand Engelbeen says:
    April 27, 2014 at 11:43 am
    I suppose that I have convinced Dr. Spencer that the increase of CO2 indeed is man-made…
    If that has much effect on temperature, that is the multi-billion dollar question which need real answers, not based on failed climate models…
    ===========================================================
    Have you reviewed the NIPCC report summaries of many peer reviewed publications on just this issue? There is, I dare say, as much, if not more, evidence that the increase of anthropogenic CO2 is likely net positive.
    This section pertains to marine life. http://www.nipccreport.org/reports/ccr2b/pdf/Chapter-6-Aquatic-Life.pdf

  49. Hi there!

    So first and most important of all, there is an important naming issue:
    The about 150GtC anthropogenic CO2 cannot have a significant effect on the oceans already containing about 36000GtC (plus being in equilibrium with the sediments containing about 3 orders more CO2), thus the oceans do not accidify due to anthropogenic inlfuence, but if at all the sea surface waters.
    Anthropogenic ocean acidification is not possible, anthropogenic Ocean surface acidification (containing about 900GtC and being in almost equilibrium with the atmosphere) is at debate.

    I think it is important to make this difference in the scientific literature, because it seems to confuse untrained readers!

    As for the mass balance argument..
    Well now that we are talking about a rather small part of the oceans (the upper 1% or less) and it is in contact with much larger reservoirs (water circulation, near shore sediments and organic CO2 deposition for example), we can only observe that the coupling constants are not kwon with sufficient precission!

    In other words: As long as models cannot predict the precise amount of deep water upwelling

    http://en.wikipedia.org/wiki/Upwelling

    and give reasons that make it believable that the transported amounts are known for the changes in ocean currents following the little ice age, the mass balance argument is flawed.

    I liked that paper linked in this article and suggest all readers to have a look:

    http://www.ncbi.nlm.nih.gov/pmc/articles/PMC3105673/

    “In conclusion, CO2 and pH in the surface ocean are not, and never have been, constant. ”

    A proper mass balance argument must be precise enough to follow these changes of the past, otherwise it is useless!

  50. Henry Clark says:
    April 27, 2014 at 10:57 am

    Admittedly, commonly shown CO2 reconstructions based on ice cores do seem to be wrong, so the debate can’t be conclusively concluded by just linking

    CO2 from ice cores is quite reliable (+/- 1.2 ppmv within the same core, +/- 5 ppmv between different cores), but the main problem is the resolution: as in your comparison of the Greenland core temperature reconstruction and the Dome C CO2 levels, the averaging for CO2 is ~560 years, more frequent sampling doesn’t give a better resolution. The resolution is the average time the pores are open to the atmosphere before the air bubbles are fully isolated from the atmosphere. That depends of the accumulation rate, which is very low at the inland cores like Dome C and Vostok. The advantage is that these cores go back up to 800 kyears. The coastal cores have a much better resolution (less than a decade for 2 of 3 Law Dome cores), but go back only 150 years for the best resolution.

    Despite this disadvantage, the ice cores overlap each other so that a nice CO2 (and CH4) trend can be seen:

    From the past, we know that the temperature influence on pre-industrial CO2 levels was about 8 ppmv/K over the ice c\ages, even over the MWP-LIA temperature change (of ~0.8 K):

    The Law Dome DSS core has a resolution of ~20 years and goes back some 1000 years, as it was drilled more downslope than the other two cores.

  51. David A says:
    April 27, 2014 at 12:15 pm

    This section pertains to marine life.

    Indeed, interesting literature. I had already read about the large changes in pH within a day inside the Great Barrier Reef and the increase of coral growth over the past 50 years. So I didn’t worry too much about the dire predictions of failed climate models, but that is a lot of up to date information…

  52. “The Law Dome DSS core has a resolution of ~20 years and goes back some 1000 years, as it was drilled more downslope than the other two cores.”

    Ferdinand, I have usually been given to understand that the accessible air spaces in the firn remain open for several decades longer than ~20years. Is this view now revised? And, if so, for what reasons?

  53. michael hart says:
    April 27, 2014 at 12:42 pm

    Ferdinand, I have usually been given to understand that the accessible air spaces in the firn remain open for several decades longer than ~20years.

    Depends of the accumulation rate. The two high resolution Law Dome ice cores have an ice equivalent precipitation of 1.2 m/year. At a depth of ~72 m the bubbles start to close. At that moment the ice is about 40 years old, the average gas age then is average 7 years older than at the atmosphere. The gas distribution thus is 50% younger than 7 years and 50% older, which has a long tail, up to 40 years, but most is within 10 years around the average.
    The air/CO2 age distribution was calculated, as that depends of firn density (= pore diameter) for the migration speed and confirmed by in-situ measurements. See fig.11 in:

    http://courses.washington.edu/proxies/GHG.pdf

  54. There are two parts of the CAGW and ocean acidification story which flatly contradict each other.

    The total mass of CO2 in the atmosphere is about one millionth of the mass of the ocean. Thus the only way that enough CO2 from the atmosphere could make a significant difference to ocean pH (even setting aside the chemical obstacles to this happening) is of the turnover and loss of CO2 from the atmosphere is fast.

    But here the problem arises because the CAGW camp is committed to very slow CO2 turnover with a very long atmosphere lifetime for other ideological reasons.

    They are trying to have their cake and eat it. The same CO2 is being asked to simultaneously stay in the atmosphere and also acidify the ocean. There is simply not enough CO2 for this. For any hypothetical chance of ocean acidification there has to be fast cycling of CO2 from the atmosphere, but this the CAGW camp cannot accept since their CO2 hellfire and damnation need to be eternal or at least persist for centuries or millenia.

    Maybe CAGW is invoking quantum mechanics with a CO2 molecule having an entangled double life in the atmosphere and the ocean at the same time.

  55. Hi Guys,
    I do appreciate the read and wanted to reply to some of the things I saw.

    First I by no means believe or support that mankind has had no impact on the increasing CO2, my statement is not nor should it be construed as an all or nothing. As it stands the equilibria relationships and marine reservoir effect would mimic the isotope ratio shift in the event that a mean increase in biological activity occurred. Humanities emissions every year amount to somewhere between 3-5% of global sources. the ocean contributes far more, something on the order of 10 or so times that of mankind’s emissions. It’s not that we haven’t contributed to the increase, I am sure we have but claiming we are solely or mostly responsible is a very long stretch, It makes the assumption that everything is balanced and the biosphere cant possibly absorb the CO2. I find it equally likely that we are the primary or sole cause of the net change, as that we are responsible for none of it.

    In response to Ferdinand Engelbeen’s comments regarding DIC and the increase or decrease in response to biolife. I don’t disagree, unfortunately your data disagrees with you. Fig. 1 of the PNAS article you linked Presents the surface measurements of pH as a function of DIC. For the top two layers DIC is going down in the bottom layer it is going up, consistent with a buffered pH decrease. While it does show the pCO2 of the atmosphere being higher than the pCO2 of the oceans most of the time, it is in fact only one site and an ecologically unique location. So while we can certainly say this site might be a sink we can also say there is a visible increase in mean biological activity.

    http://www.pnas.org/content/106/30/12235.full.pdf

    This is not in any way reflective of other sites like the arctic, which large changes in biological production in the summer months and almost no absorption in the winter months. Nor does it reflect areas where there is a convergence of fresh and saltwater.

    Like I mentioned this would be plausible mechanism by which we can see an increase in CO2 via natural sources. At this time we don’t have sufficient data to prove or disprove the hypothesis.

  56. George.E.Smith, on measuring gases, the difference between ppm by mass and ppm by volume is just accounting. But because the ideal gas equation applies at most atmospheric conditions, it is more convenient to do volume accounting. For instance, an analyzer might use a fixed volume loop, typically on the order of 1 mL, as the basis for measurement. This is easier to handle, than say measuring the mass of such as small sample size (one doesn’t have to worry about buoyancy, etc. Further, one can blend two or more gases dynamically by combining measured flow rates of those gases, which is also easy to determine. One can fix one flow rate and vary the second over a wide span for calibration, etc. It is more difficult and requires more specialized equipment to combine gases in a cylinder and weigh them (although this can as is done).

  57. Hoser says:
    April 27, 2014 at 10:22 am

    You were going down a fruitful path with biological responses, and then you left it. People forget about biology, and that’s often where chemists and physicists go awry when they deal with processes on Earth
    ==============

    Right you are, and case in point is the generally accepted explanation for the bi-yearly cycling of atmospheric CO2 ppm, which for the past 56 years, measurements have determined that is has increased an average of 8 ppm during the Northern Hemisphere fall/winter months of October thru March …. and decreased an average of 6 ppm during the spring/summer months of May thru September, thus resulting in an average yearly increase of 2 ppm.

    Thus the generally accepted explanation for the above is: 1) the 2 ppm average annual increase in CO2 is a direct result of increases in human emissions; 2) the bi-annual average decrease of 6 ppm during the spring/summer months is a direct result of biomass growth in the Northern Hemisphere; and 3) the bi-annual average increase of 6 ppm during the fall/winter months is a direct result of dead biomass decomposition (rotting/decaying) in the Northern Hemisphere;

    Now the above sounds fine and dandy, …… but, in my opinion, number 1) is highly questionable.

    And biologically speaking, numbers 2) and 3) are highly improbable if not impossible accusations ….. simply because the rotting and decaying of dead biomass is highly dependent upon moisture (liquid water) and temperature.

    The spring/summer is optimum time for the rotting and decaying of dead biomass because there is adequate moisture and surface temperatures are above 60 F. Bacteria, yeasts and fungi thrive in said conditions.

    The fall/winter is not conducive to the rotting and decaying of dead biomass because of the normally dry conditions during the months of September and October. Bacteria, yeasts and fungi DO NOT thrive in dry conditions.

    Dried foods (biomass) will keep for several years.

    When fall/winter temperatures are below 60F, the rotting and decaying of biomass is severely affected. When said temperatures are below 42 F then the rotting and decaying of biomass is severely restricted. When said temperatures are below 32 F then the rotting and decaying of biomass is pretty much non-existent.

    Cellar house or cooler kept foods (biomass) will keep for several days.

    Refrigerated foods (biomass) will keep for several weeks.

    Frozen foods (biomass) will keep for several years.

    Bacteria, yeasts and fungi produce very little to no CO2 during cool, cold and/or frozen conditions. They abide by the Refrigerator/Freezer Law of Biomass Decomposition …. and the USDA recommends that you abide by it also. And Public Health Departments demand that public entities strictly abide by it.

    The steady and consistent 56 consecutive years of bi-yearly cycling of atmospheric CO2 ppm is in dire need of a better explanation.

  58. phlogiston says:
    April 27, 2014 at 3:35 pm

    There are two parts of the CAGW and ocean acidification story which flatly contradict each other.

    The two parts are not in contradiction if you make a distinction between the ocean’s “mixed layer”, the upper few hundred meters of the oceans, and the deeper oceans. The mixed layer and the atmosphere are in close contact with each other and exchange CO2 by wind and convection within a year half life time. The ocean currents that are exchanged between the mixed layer (and the atmosphere) and the deep oceans are much more limited.

    Both the atmosphere and the mixed layer have about the same CO2 content: resp. 800 and 1000 GtC. But the 30% increase in the atmosphere only induces a 3% increase in the mixed layer, due to the Revelle/buffer effect. But that is enough to lower the pH somewhat…

    The exchanges with the deep oceans and vegetation are a lot slower: not the seasonal exchanges (which are enormous), but these are quite fixed in quantity and temperature dependent. Any excess CO2 in the atmosphere will go down in the deep oceans (and vegetation) as a result of the extra CO2 pressure increase in the atmosphere, but that is only halve the amount humans emit per year…

  59. Steven Burnett says:
    April 27, 2014 at 3:38 pm
    It makes the assumption that everything is balanced and the biosphere cant possibly absorb the CO2…
    =====
    Which common sense tells you if CO2 can drop from the thousands to the 200’s…the sinks are no where near full and no amount of CO2 produced by man could ever fill them or could ever accumulate…
    Something else is making CO2 levels rise…something is making the sinks release CO2

    …I think it’s biology

  60. Steven Burnett says:
    April 27, 2014 at 3:38 pm

    Fig. 1 of the PNAS article you linked Presents the surface measurements of pH as a function of DIC. For the top two layers DIC is going down in the bottom layer it is going up, consistent with a buffered pH decrease.

    The figure shows the (calculated and measured) pH trend, not the DIC trend. If DIC increases (as is mentioned in the text further on), the pH decreases… That also shows that the DIC increase is solely in the upper layers and not caused by biolife, because that would decrease DIC in the uppermost layer near the surface and increase it in the intermediate layer.

    Further there are now over two million measurements from a lot of places over many oceans, from ships surveys and buoys. That shows that the average pCO2(atm) is higher than the average pCO2(aq). The compilation of the first near-million measurements is here:

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

    Last but not least: the much higher 13C/12C ratio of ocean CO2 simply excludes the oceans as source of the extra CO2 while the 13C/12C ratio of the atmosphere and ocean surface layer goes down in lockstep with the release of fossile CO2…

  61. Samuel C Cogar says:
    April 27, 2014 at 4:10 pm

    That the biosphere is responsible for the seasonal swings is proven: the oxygen and 13C/12C ratio go up and down together with the CO2 variation: in spring oxygen goes up while total CO2 goes down (around the upgoing trend) and the 13C/12C ratio goes up, because the preferential use of 12CO2 by growing plants. The opposite happens in fall. While much debris is decayed over longer term (somewhat more in summer than in winter), a lot of chemicals like leaf parts are easely broken down within weeks. Over a winter, even under snow, a whole pile of composting material can shrink to halve its size… And measurements in Alaska did show a lot of CO2 release from under the snowdeck even at -40 C…

    Further, there is less land/forest in the SH than in the NH and there is far less seasonal variation in the SH…

  62. “”””””…..

    R. Shearer says:

    April 27, 2014 at 3:53 pm

    George.E.Smith, on measuring gases, the difference between ppm by mass and ppm by volume is just accounting. But because the ideal gas equation applies at most atmospheric conditions, it is more convenient to do volume accounting. For instance, an analyzer might use a fixed volume loop, typically on the order of 1 mL, as the basis for measurement. …..”””””

    So if I collect 1 ml of atmosphere at roughly sea level at STP, and I remove all the CO2 molecules, and none of any other non-CO2 molecules, and then adjust the T&P of the CO2 sample to STP, I would expect about 1/2500 of a ml, which is about 737 micron, and if I wanted to measure that to about 0.1 ppm, since that is the order of the data plotted for ML, how do I measure such a small volume, so accurately.

    But I’m more concerned about how I get all of the CO2 molecules out of the 1 ml, and not even one, of any other species.

    I would place a whole lot more credibility in a specification of the relative molecular abundance, rather than any relative volumes.

  63. Ferdinand Engelbeen says:
    April 27, 2014 at 4:11 pm
    “Any excess CO2 in the atmosphere will go down in the deep oceans (and vegetation) as a result of the extra CO2 pressure increase in the atmosphere, but that is only halve the amount humans emit per year…”

    Here we have a local example of unexpected upwelling affecting the surface of the oceans , where the opposite is happening, the reason for the bad oyster harvest described here:

    http://e360.yale.edu/feature/northwest_oyster_die-offs_show_ocean_acidification_has_arrived/2466/

    is not anthropogenic, would you agree?
    In this case we have a local acidification of which would be driven by an ocean current and within a short time span it will be in near equilibrium with the atmosphere.
    Looking at a slightly larger piece of the oceans, then your precious mass balance will also be valid for any given time, while the reason for this local acidification is still not anthropogenic.
    In my opinion this real example disqualifies the mass product as an example as long as natural fluxes (and fluctuations) are known and predictable.

    May I repeat my pledge for a precise language and to make a difference between ocean acifidication and ocean surface acidification!

    Anthropogenic ocean acidification is not possible, anthropogenic ocean surface acidification (containing about 900GtC and being in almost equilibrium with the atmosphere) is at the debate.

  64. For all that we should sceptical about many of the claims made in support of CAGW theory, no-one is going to persuade me that we’re not contributors of CO2 to the atmosphere…

    • At 2:07 AM on 28 April, Pete Brown had earnestly written:

      For all that we should [be] sceptical about many of the claims made in support of CAGW theory, no-one is going to persuade me that we’re not contributors of CO2 to the atmosphere…

      Are you susceptible to persuasion on this issue at all? If that’s the case, be persuaded that the CAGW conjecture (which has never risen to the level of “hypothesis,” much less “theory,” in terms of methodological rigor) had been preposterous ab ovo, and that those who keep trying to peddle it – even today, 17 years into the “pause” and getting on to five years after the first Climategate exposures confirmed the long-held suspicions of the “climate consensus” moral turpitude and ethical bankruptcy – have not only failed to provide the levels of evidentiary support required when so plainly contrafactual a contention is advanced but also to address the deliberate evasion of error-checking that has raddled their methods of investigation.

      Beyond that, of course, there’s no argument that purposeful human action doesn’t contribute to atmospheric CO2 content, but rather the absence of evidence that this particular source of atmospheric CO2 (trivial as it truly is, in comparison to CO2 emissions wholly and forevermore beyond human causation or control) has had – or could ever have – any significant climatological impact whatsoever.

      Zip. Nada. Bupkis. Squat. Blank-o-la. Not there. Tooth fairy and Santa Claus and Soebarkah’s birth certificate. Not just “can’t find it” but “never happened.”

      Not even a circumstantial connection. And the more we look into it, the better honest men can appreciate that circumstantiality didn’t really happen all that much, either.

      You’re not being asked to take up pitchforks and torches and hot tar and poultry offal en route to Collegetown, PA, and the lair of Hide-the-Divide Mann.

      Of course, someone with a decent regard for the scientific method wouldn’t have to be asked.

  65. Volcanic CO2 is by far the largest natural CO2 producer at varying rates. What has been missed is the ocean ridge volcanism which injects vast volumes of CO2 into the ocean floor waters. The circulating waters are around 400C with a pH of around 4.0. The life using chemical instead of light energy around these vents thrive in these high acid conditions. Despite this acidic inject oceans remain with an average pH 7.5-8.4.

  66. Lots or errors in the process, you aren’t suffering from Lipitor derangement syndrome are you? I seem to notice a tendency in myself.

  67. Henry’s-law constant H for CO2 -water solutions is 1.42×10^3 atm/mole fraction at 20 C. Using simple Henry’s-law solubilities (p=H*x), the oceans should hold only 30% of the 2,900 giga tonnes of the atmospheric CO2 at equilibrium, but the actual figure is >50 times this amount. In fact, for an ideal vapour-liquid equilibrium system obeying Raoult’s law, an atmospheric pressure of 175 atmospheres would be required to contain this colossal amount (50*2,900=145,000 giga tonnes) of CO2in the oceans. The majority share of CO2 is taken up by the oceans competing with the biosphere’s CO2 requirements for plant growth and food supply. Non-ideality accounts for its large solubility in water and clearly it is sequestered and fixed by chemical and biological reactions. They involve the formation of carbonate rocks and phytoplankton growth through photosynthesis. The reactions remove dissolved CO2 from the equilbrium equation, driving it to the right, thereby giving the oceans a near limitless ability to absorb CO2.

    Acidity

    Rainwater condensing from cloud formations dissolves CO2 to form weak carbonic acid, it always has and it always will. It has been responsible for stalactites and stalagmites in caves over thousands of years. Rainwater of course is initially pure water in which there are few ionic species; seawater however is quite different and contains many soluble cations and anions. Sodium and magnesium, which will form stable crystalline solid bicarbonates, are present in abundance. Carbon dioxide in seawater yields salts such as sodium carbonate which are soluble in water and are hydrolysed in solution thus:

    Na2CO3 + H2O = NaHCO3 + NaOH

    and their solutions are in fact alkaline. For the anti carbon green warmist lobby and the BBC to pronounce that the simple addition of carbonic acid or dissolution of CO2 in seawater will make it acidic is nonsense and he clearly does not understand the complex ionic system pertaining in the oceans. The capacity of seawater to buffer pH changes is well known and its pH always remains in range 7.5 to 8.4 which is alkaline.

    Life Force

    In addition of course, as stated, it is essential to life in the biosphere and our very existence depends on it. So to declare CO2 a pollutant to be somehow eliminated from the environment is stupid and dangerous when in fact increased CO2 does increase the growth rates of plants and also permits plants to grow in drier regions. Animal life, which depends upon plants, also flourishes, and the diversity of plant and animal life is increased. Human activities are producing part of the rise in CO2 in the atmosphere. Carbon in coal, oil and natural gas is being moved to the atmosphere, where it is available for conversion to living things.

  68. Forensic pathologists are experts in rate of human tissue decay. Could there be some help/information in that quarter in studying biotic decay in the oceans?

  69. Laws of Nature says:
    April 27, 2014 at 6:07 pm

    Looking at a slightly larger piece of the oceans, then your precious mass balance will also be valid for any given time, while the reason for this local acidification is still not anthropogenic.

    Besides the seasonal exchanges 50 GtC in and out between the ocean surface and the atmosphere, there is a near permanent exchange of about 40 GtC/year with the deep oceans, The main sinks are near the poles and especially in the NE Atlantic Ocean (the sink place of the THC). That travels in the deep to beyond South America and pops up near the equator amongst the Chilean coast. Near the poles, the cold waters are far undersaturated in CO2 and take a lot of it with the THC into the deep. At the warm equator, the upwelling waters are oversaturated with CO2 and release a lot of it at the temperature near the equator. The total exchange in and out is around 40 GtC/year. There is some natural variability in the seasonal and permanent exchanges, but that is not more than +/- 2 GtC around the trend over the years. Human emissions are currently near 10 GtC/year…

    What happens if there is a disequilibrium between the inflows and outfows of the deep oceans is that the level in the atmosphere will increase or decrease until the original in/outflux is back into equilibrium. The opposite also may happen: as humans increase the levels in the atmosphere, more will pushed into the cold polar sinks and less will be emitted at the warm upwelling places.

    How do we know which one is at work? By looking at the isotopic ratio. Pre-Industrial there was an isotopic equilibrium between oceans, vegetation and atmosphere at about -6.4 per mil δ13C, now we are at -8 per mil. The oceans are at 0 to +5 per mil, fossil fuels are average at -24 per mil…

  70. Latitude says:
    April 27, 2014 at 4:33 pm

    Which common sense tells you if CO2 can drop from the thousands to the 200′s…the sinks are no where near full and no amount of CO2 produced by man could ever fill them or could ever accumulate…

    You forget the time frame: during the onset of a deglaciation it did take 5,000 years to release 100 ppmv CO2 and 10,000 years to absorb it again when the world was getting into a new cold period. Now humans have added near 200 ppmv CO2 over only 160 years. Something says to me that nature can’t absorb that all within a short time.

    That is confirmed by the sink rate: the current sink rate shows that some 4.5 GtC/year is removed from the atmosphere. The pressure difference at the current temperature is about 100 ppmv (=210 GtC) above equilibrium. That gives an e-fold time of ~52 years or a half life time of ~40 years for the removal of the excess amount of CO2 in the atmosphere. Fast enough to follow the ice ages, but too slow to remove all human input in short time…

  71. As a field geologist my abilities are empirical rather than theoretical. I can see Devonian age [about 420Ma to 358Ma] rocks in the field. In places they are incredibly fossiliferous. The fossil Devonian carbonate reefs of the Kimberley region in Western Australia are stunning. Armoured fish were common.
    All these creatures were living happily in seas that were in equilibrium with an atmosphere that had CO2 levels up to ten times, or more, greater than present day.

    There is obviously great deal of buffering in the world’s oceans and catastrophic general acidification doesn’t happen.

  72. Ferdinand Engelbeen says:
    April 28, 2014 at 4:58 am

    “Besides the seasonal exchanges 50 GtC in and out between the ocean surface and the atmosphere, there is a near permanent exchange of about 40 GtC/year with the deep oceans,
    [..]”
    I understand this is your opinion.. too bad for the 2011 west coast oysters that it is not so constant in reality..
    “What happens if there is a disequilibrium between the inflows and outfows of the deep oceans is that the level in the atmosphere will increase or decrease until the original in/outflux is back into equilibrium. The opposite also may happen: as humans increase the levels in the atmosphere, more will pushed into the cold polar sinks and less will be emitted at the warm upwelling places.

    How do we know which one is at work? By looking at the isotopic ratio. Pre-Industrial there was an isotopic equilibrium between oceans, vegetation and atmosphere at about -6.4 per mil δ13C, now we are at -8 per mil. The oceans are at 0 to +5 per mil, fossil fuels are average at -24 per mil…”

    No Sir, the isotopes cannot tell you this! All they tell you is, that we are indeed burning fossil fuel and it is partially diffusing into the oceans.
    My real example showed local acidification due to natural causes and thus falsifies you mass balance argument for that region.
    You seem to assume that the ocean currents do not affect the ocean surface water CO2 concentration, while the reality clearly indicates otherwise.. for the small amout of time we have any data that is

  73. Ferdinand Engelbeen says:
    April 27, 2014 at 5:23 pm
    “Over a winter, even under snow, a whole pile of composting material can shrink to halve its size…

    Some years ago we bought a property that had about 3 acres (hectare+) of Spotted Knapweed (Centaurea stoebe). I borrowed a tractor with a sickle bar and cut the “crop.” Then I raked and piled it up, reaching about 8 feet high and twice as wide. From a nearby dairy I hauled 3 pickup loads of fresh manure and covered the pile of weeds. We get about 8 inches of precipitation per year, about half rain and half snow – during cold winters and hot summers.
    After about 7 years there was a very small hump left on the ground where the pile of weeds and manure had been. Had I known 25 years ago that this subject would come up – I would have kept precise records.

  74. Henry Clark says:
    April 27, 2014 at 7:24 am

    “So, as stands about the preceding, civilization emits enough CO2 to be about double the measured rise of it in the atmosphere.”

    A meaningless observation in a dynamic system.

    “…but, if you look at the plots of temperature driven CO2 release in ice age cycles…”

    Long term and short term responses are not the same. See Salby’s lecture.

    “The former is mainly merely going in a loop.”

    Nature is not a reciprocating pump. There is a drain in your container.

    Werner Brozek says:
    April 27, 2014 at 9:02 am

    The rate of change of atmospheric CO2 is still in lockstep with the temperature “pause”. It’s not anthropogenic.

    There is absolutely no doubt about this. But, I have despaired of trying to convince people who do not want to recognize what is staring them in the face. Small wonder we have such a fiasco unfolding with just the warming part having taken a powder, when even skeptical people avert their gazes from what hard data are telling us, and prefer to hew to the narrative made up only of what people think should be happening.

    Watch and see what happens. Within maybe 5 years, the rate of change will still be languishing with temperatures, while human inputs will have soared to even greater heights. Maybe then, the truth of the matter will gain some traction. The divergence is already well on this way. The plot at that link is a couple of years old now, and as seen at the previous link, the relationship with temperatures is still holding.

  75. Laws of Nature says:
    April 28, 2014 at 9:23 am

    No Sir, the isotopes cannot tell you this! All they tell you is, that we are indeed burning fossil fuel and it is partially diffusing into the oceans.

    LoN, the overall picture is clear. If the CO2 increase was from the oceans, the 13C/12C ratio of the atmosphere would go up, not down.

    Anyway, where deep ocean waters are upwelling, CO2 will be released if the surface temperature is high enough. Which is the case for the oyster hatchery you were referencing. That happens sometimes at several places along the coasts and more permanently along the Peruan/Chilean coast, except during an El Niño.

    Local carbon balances are extremely difficult to calculate, even with more and more “tall towers” which measure the CO2 fluxes over hundreds of meters height from a large area. There is some hope that the Japanese satellite will show regional CO2 fluxes over land and sea with a better resolution.

  76. Now humans have added near 200 ppmv CO2 over only 160 years. Something says to me that nature can’t absorb that all within a short time.
    =====
    Here we agree to disagree….
    Where we differ is I truly believe CO2 levels were low enough to be limiting….just like adding CO2 to a greenhouse in the 1000’s ppm, only for it to drop to limiting again in less than one day…or for that matter, having to continuously add CO2 to any system dependent on it…..

    You can’t realize that the planet is “greening”….without realizing that

    I do agree with you that a ‘very’ small part of the CO2 rise is due to man’s actions…..but that is more land use, crop use (c4’s), fertilizer (nitrogen) use, irrigation, bacteria, etc and the effect that has on the c12/c13 ratio…adding water and nitrogen to the nitrification/denitrification bacterial cycle etc
    I also realize that trying to divine fuels from that ratio is one of the biggest scams going…

  77. Bart says:
    April 28, 2014 at 10:41 am

    Hi Bart, we have been there many times…

    In short, for those who are new here: the variability of the rate of change of CO2 is in lockstep with the temperature variability. But because human emissions are about twice the average increase of CO2 in the atmosphere and the law of conservaiton of mass, the variability in increase rate of CO2 in the atmosphere caused by temperature is a variability in sink rate, not in source rate.

    Despite the overall mass balance, there is an escape possible for Bart’s theory: if the global carbon cycle for some reason increased in lockstep with human emissions. If the sinks have a huge capacity, then the increase of circulation will give an increase of CO2 in the atmosphere, while dwarfing the human emissions.

    There are several problems with that theory: there is not the slightest indication that the carbon cycle increased in intensity, to the contrary: the latest estimates of the residence time (= residing mass / throughput) show a small increase over time, which would be the case if the troughput remained the same for an increased mass of CO2 in the atmosphere.
    And as the biosphere is a net sink (of ~1 GtC/year) for CO2, only the oceans are the main possible cause of the increased circulation. But that violates the measured 13C/12C trends, which go opposite to the theory…

    Further, there is not the slightest problem with divergence: the calculated absorption of CO2 in the oceans, based on the pressure difference between observed CO2 levels and equilibrium CO2 levels in the atmosphere still is widely within natural variability:

    The red line is the calculated trend.

  78. E.M.Smith says:
    April 28, 2014 at 11:23 am

    @Latitude:

    Yup. “Has issues”: https://chiefio.wordpress.com/2009/02/25/the-trouble-with-c12-c13-ratios/

    Also, plants pull atmosphereic CO2 down to starvation levels if left to their own devices for long:

    https://chiefio.wordpress.com/2010/10/10/got-wood/

    ANY forest has sequested more CO2 than is above it. By a long shot.
    ======
    Excellent!….why didn’t you tell me that sooner? Read it all, damn you got every bit of it too!

    don’t forget the methane cloud over the Amazon……….it’s what bacteria do when you feed them (carbon)

  79. Ferdinand Engelbeen says:
    April 28, 2014 at 10:49 am
    “[..]LoN, the overall picture is clear. If the CO2 increase was from the oceans, the 13C/12C ratio of the atmosphere would go up, not down.[..]”
    No Sir, the isotope depletion is related to the anthropogenic influx and I repeat myself has not necessarily anything to do with the CO2 levels.

    Just like when you pee in a snow hill the anthropogenic influx might increase the frozen water amount or decrease it, but that depends on other conditions – in any case: Never eat yellow snow

    As for the mass balance you repeat two posts later.. I have already shown you a real example, where a natural upwelling are the (local) cause for an increase of CO2 in the upper ocean an the atmosphere and you can keep the mass balance intact just by taking a bigger part of the ocean into consideration and the mass balance argument fails completely for this local event – it is worthless (just like Essenhigh had already shown years ago on global scale)

  80. Before you get much further with this, you may want to take a look at the work of Roger Revelle on the buffering capacity of the oceans, or perhaps Revelle Revisited is an easier paper to find on the net. The long and the short of it is that the four reactions you are considering would predict that the pH of the oceans was below 7, but it is really ~8, because of the other species mixed in.

    As to how far back one can trace ocean pH, never fear, there are proxies True the acid concept is relatively new, and electrochemical methods of measuring pH date back only to 1906. How it is possible, then, that we have measurements of pH going back more than 250 years. The answer is that there are biogeochemical proxies for pH including, among others, boron isotope ratios of foraminiferal carbonate, which can take us back much further than 250 years.

  81. E.M.Smith says:
    April 28, 2014 at 11:23 am and
    Latitude says:
    April 28, 2014 at 12:07 pm

    Indeed it is impossible to make a direct differentiation between the burning of fossil fuels and the decay of current biomass. But what you forget is that both use oxygen. Fossil fuel use is known within reasonable limits and burning efficiency of the different fuels is known too. Thus one can calculate the amount of oxygen used by burning fossil fuels.

    Since about 1990 the analytical techniques are accurate enough to measure the necessary difference of less than 1 ppmv on 200,000 ppmv oxygen. That did show that the biosphere as a whole (land en seaplants, microbes, insects and all kind of animals) produces a small amount of oxygen, as the decrease of oxygen in the atmosphere is less than what is calculated from fossil fuel use. Thus it doesn’t matter one damn thing what kind of plants (C3 or C4) are gobbling CO2: the whole biosphere is a net sink for CO2 and preferably 12CO2, thus leaving relative more 13CO2 in the atmosphere. Thus not the cause of the 13C/12C decline in the atmosphere. See:

    http://www.bowdoin.edu/~mbattle/papers_posters_and_talks/BenderGBC2005.pdf

    Even if you don’t like the oxygen data, it is known from satellite measurements that the earth is greening, thus storing more CO2 than it releases.

    As the oceans are a lot higher in 13C/12C ratio, they are not the cause of the 13C/12C decline either.

    Conclusion: the 13C/12C decline is fully caused by the burning of fossil fuels.

  82. is there any credit given to anything that would produce 13CO2 other than fossil fuels?

    …because there is

  83. Ferdinand Engelbeen says: April 27, 2014 at 5:23 pm

    That the biosphere is responsible for the seasonal swings is proven: the oxygen and 13C/12C ratio go up and down together with the CO2 variation:
    ————————

    How can that be when it was previously stated that burning fossil fuels is responsible for the 13C/12C ratio going down and the CO2 ppm going up?

    Fossil fuels are being burned all year round therefore the 13C/12C ratio should be going down all year round, …… should it not?

    Anyway, would not the sequestering of the 13C not be an adequate explanation for the 13C/12C ratio going down? I think it would, and I think I pointed this out to you before, to wit:
    —————-

    “Differences in altitude are also known to affect terrestrial plant carbon isotopic signatures (δ13C) in mountain regions, since plant δ13C values at high altitudes are typically enriched (Körner et al. 1988; 1991) compared to the carbon signatures of plants from low altitudes. Soil organic matter also show enrichment in 13C with soil depth, which is suggested to be a consequence of humification and the loss of the lighter isotope (12C) via respiration, thus concentrating 13C in the soil organic matter (Kramer et al. 2003).

    http://www.diva-portal.org/smash/get/diva2:303212/FULLTEXT01.pdf

    DUH, sequestering the 13C in the soil and the woody portion …… and respiring the 12C into the atmosphere.
    ================

    Ferdinand Engelbeen says: “ in spring oxygen goes up while total CO2 goes down
    —————–

    What do you mean by “in spring”?

    Did you mean “spring” aka: the spring equinox? “spring” aka: warm temperatures; or “spring” aka: both spring and summer?

    When talking about the START of the bi-yearly decrease in CO2 …. relative to the START of the “spring” biomass growing season …..you can not be talking in “generalities” because it only confuses the issue and affords the speaker a lot of “slack” to prove or justify their claim.

    The start of “spring” biomass growth is determined by the amount of daily Sunlight …. and the rate of growth is determined by the ambient temperature and the amount of moisture. The initial growth is not dependent upon atmospheric CO2 but on stored sugars in the roots or the seeds. Thus, growing biomass does not absorb any CO2 until is has grown sufficient foliage (leaves) to do so. And it only absorbs maximum CO2 after it has grown its maximum foliage and then only in full Sunlight. Cloudy, rainy, cool, dark and/or dry/drought conditions retards photosynthesis.

    And the “local specific” start of “spring” biomass growth progresses from the lower latitudes to the higher latitudes as the Sun moves north of the Equator. Reference this “temperature zones” map: http://www.waldeneffect.org/20100313frost.jpg

    And the same “conditions” that permits the spring” biomass growth to progresses from the lower latitudes to the higher latitudes ….. are the same “conditions” that permits the rotting and decaying of the dead plant biomass to progresses from the lower latitudes to the higher latitudes. Thus, CO2 is being emitted into the atmosphere and absorbed from the atmosphere at the same time.

    But, the Mona Loa Record is factual proof that Atmospheric CO2 always reaches its maximum ppm in mid-May of each year …. except for like 7 or 8 of the past 56 years. To wit:

    NOAA’s complete monthly average Mona Loa CO2 ppm data
    ftp://aftp.cmdl.noaa.gov/products/trends/co2/co2_mm_mlo.txt

    Now, given all the above variables, if plotted on the referenced “temperature zones” map, how does one explain the Mona Loa data with the maximum atmospheric CO2 ppm occurring in mid-May of most every year ….. especially when like only 50% of the new growth biomass, as per the afore cited “temperature zones” map, … has reached “full foliage” status by mid-May?

    And ps, if you check that Mona Loa Record you will note that the minimum atmospheric CO2 ppm has occurred at the end of September of most every year for the past 56 years.

    Now how do you explain that coincidence? Surely not by the “starting” point of your presumed “rotting and decaying” of biomass. Remember now, those microbes only “work” when the temperature and moisture are to their liking.

  84. Laws of Nature says:
    April 28, 2014 at 12:22 pm

    the mass balance argument fails completely for this local event – it is worthless (just like Essenhigh had already shown years ago on global scale)

    The mass balance doesn’t work for local events, simply because one doesn’t know all local inputs and outputs. But for a global mass balance, one doesn’t need that: without knowing one natural in/outflow one can know the balance at the end of a year: human CO2 emissions are known, the increase of CO2 in the atmosphere is known, the difference is known, all with reasonable accuracy: around 45% of the extra induced CO2 as mass (not as original molecules) is removed somewhere in natural sinks.

    And sorry, but Essenhigh confused residence time (which is ~5 years) with the removal rate of an excess amount of CO2 in the atmosphere (which needs ~50 years e-fold time)…

  85. thus leaving relative more 13CO2 in the atmosphere….

    Ferdinand, methane reduction, nitrification, and denitrification are all net producers of 13CO2……
    …..bacteria

    We are using it to monitor the dead zones..

  86. Samuel C Cogar says:
    April 28, 2014 at 3:08 pm

    Samuel, please, the seasonal swings are around the trend, the trend itself may be up, down or flat, that has nothing to do with the seasonal swings…

    The seasonal swings at Mauna Loa are +/- 3 ppmv, while the trend is only 2 ppmv/year,

    Further the “enrichment” of plants at high altitude with 13C is relative to plants at lower altitude, but still way below what can be measured in the air: that is clearly visible in the graphs and table of the reference you gave.

    And for the timing: it takes some time for the CO2 peak to reach the 3,400 m height of Mauna Loa:

    but even Barrow is quite late in the game, as it takes more time for thawing and growing and it is also faster ending its growing season. More data can be found for different places at:

    http://www.esrl.noaa.gov/gmd/dv/iadv/

    But in general, the exact timing of the CO2 peak and 13C/12C ratio minimum is a matter of equilibrium between CO2 uptake by vegetation and release of CO2 from soil bacteria etc. Plus a shift in peak timing due to the continuous release of 13C depleted CO2 by humans.

    Anyway it is clear that the seasonal swings are caused by vegetation growth/decay, because if it was from the ocean warming/cooling, then CO2 and 13C/12C ratio should both go up and down in parallel.

  87. Latitude says:
    April 28, 2014 at 3:13 pm

    Ferdinand, methane reduction, nitrification, and denitrification are all net producers of 13CO2……
    …..bacteria

    Yes, but if that adds to the atmosphere, these sources can’t be the cause of the decrease of the 13C/12C ratio in the atmosphere… Only if the methane is oxydised, it will add to the 13C depletion. But there is little change in CH4 levels in the atmosphere over the past decade, thus little change in production of methane…

  88. Ferdinand Engelbeen says:
    April 28, 2014 at 3:12 pm
    “The mass balance doesn’t work for local events, simply because one doesn’t know all local inputs and outputs. But for a global mass balance, one doesn’t need that:[..]
    And sorry, but Essenhigh confused residence time (which is ~5 years) with the removal rate of an excess amount of CO2 in the atmosphere (which needs ~50 years e-fold time)…”

    Well, now we agree on the local event where the mass balance fails, because the fluxes are not known precisely enough! Time to address my first comment here:
    Laws of Nature says: April 27, 2014 at 12:17 pm
    “As for the mass balance argument..
    Well now that we are talking about a rather small part of the oceans (the upper 1% or less) and it is in contact with much larger reservoirs (water circulation, near shore sediments and organic CO2 deposition for example), we can only observe that the coupling constants are not kwon with sufficient precission!”
    So, I guess we can agree that IF the fluxes on a global scale WERE not known with sufficient precission your statement WOULD have to be expanded over all arguments, this is exactly what Essenhigh shows:
    Beside the fact that anthropogenic influx into the ocean surface water is bigger that the “outgasing” at any given time, this reservoir could still be controlled and dominated by deep sea influx. Naming issues do NOT make this clear result go away.

    Think of the pee in a snow hill (sorry for the graphic image), if this clearly identifiable anthropogenic influx leads to additional frozen water or a local meltdown depends on other conditions and influxes.

  89. Laws of Nature says:
    April 28, 2014 at 7:03 pm

    “Well now that we are talking about a rather small part of the oceans…”

    Indeed, that is the flaw in the so-called “mass balance” argument. It’s a shell game. They assume a closed system, but then eliminate unknown portions of the system from consideration. You are supposed to ignore that, that prestidigitation reduces the problem to an open subsystem, and a mass balance argument no longer applies.

  90. Ferdinand Engelbeen says:
    April 28, 2014 at 4:12 pm

    Samuel, please, the seasonal swings are around the trend, the trend itself may be up, down or flat, that has nothing to do with the seasonal swings…

    The seasonal swings at Mauna Loa are +/- 3 ppmv, while the trend is only 2 ppmv/year,
    —————–

    Ferdinand, are you trying to bedazzle me with your above tripe and piffle ….. or what? I could care less about your “swings” and ”trends” because I am not a proponent of “junk science” crapolla. I am fully aware of what the cited Mona Loa data signifies …. so address my argument and cease with your obfuscations.
    ==============

    And for the timing: it takes some time for the CO2 peak to reach the 3,400 m height of Mauna Loa:
    ——————-

    Really now, Ferdinand, and just how long does it take for the maximum emissions of surface emitted CO2 to reach the 3,400 m height of Mauna Loa? And is that the same amount of time that it takes before the minimum emissions of surface emitted CO2 is detected at the 3,400 m height of Mauna Loa?

    And so what, biomass growth starts in the lower latitudes like two (2) months before the Sun crosses the Equator on March 20/21 at the Vernal Equinox. And biomass growth stops in the northern latitudes like two (2) months before the Sun re-crosses the Equator on September 22/23 at the Autumnal Equinox.

    But none of the above explains the steady and consistent 56 consecutive years of the bi-yearly cycling of CO2 as defined by the Keeling Curve Graph simply because of the non-predictable surface conditions during the spring and fall of each year.

    IF, … there has been a CO2 caused INCREASE in global average temperatures over the past 60 years ….. that has subsequently caused a DECREASE in the length of the winter season (Nov thru March) …. then the aforesaid combined INCREASE/DECREASE should be reflected in/by an INCREASE in the average ppm amount of bi-yearly cycling of CO2 and/or an INCREASE in the length of the decreasing CO2 cycle…. simply because if the winter season decreases then the biomass growing and decaying season increases.

    And if there has been such a change in the bi-yearly cycle then it can not be attributed to “human caused” …… because humanity doesn’t do anything “steadily and consistently” on a bi-yearly cycle for 56 consecutive years. And “fuzzily” calculated mathematics is not going to prove otherwise ……. whereas statistics will, to wit:

    Increases in World Population & Atmospheric CO2 by Decade

    year — world popul. – % incr. — Dec CO2 ppm – % incr. — avg increase/year
    1940 – 2,300,000,000 est. ___ ____ 300 ppm
    1950 – 2,556,000,053 – 11.1% ____ 310 ppm – 3.1% —— 1.0 ppm/year
    1960 – 3,039,451,023 – 18.9% ____ 316 ppm – 3.2% —— 0.6 ppm/year
    1970 – 3,706,618,163 – 21.9% ____ 325 ppm – 2.7% —— 0.9 ppm/year
    1980 – 4,453,831,714 – 20.1% ____ 338 ppm – 3.8% —– 1.3 ppm/year
    1990 – 5,278,639,789 – 18.5% ____ 354 ppm – 4.5% —– 1.6 ppm/year
    2000 – 6,082,966,429 – 15.2% ____ 369 ppm – 4.3% —– 1.5 ppm/year
    2010 – 6,809,972,000 – 11.9% ____ 389 ppm – 5.1% —– 2.0 ppm/year
    2012 – 7,057,075,000 – 3.62% ____ 394 ppm – 1.3% —– 2.5 ppm/year per 2 years

    Source CO2 ppm: ftp://aftp.cmdl.noaa.gov/products/trends/co2/co2_mm_mlo.txt
    =================

    But in general, the exact timing of the CO2 peak and 13C/12C ratio minimum is a matter of equilibrium between CO2 uptake by vegetation and release of CO2 from soil bacteria etc. Plus a shift in peak timing due to the continuous release of 13C depleted CO2 by humans.
    —————-

    YADA, … YADA, … YADA, ….. you are obfuscating again. I talk science, …. not associations, correlations, estimations, insinuations, guesstimations, etc.

  91. But there is little change in CH4 levels in the atmosphere over the past decade, thus little change in production of methane…
    ——————–

    HA, …. they have been “punching” new holes in the ground over the past 15+ years like they are going out of style. And the “No Smoking” rules anywhere near the “wellhead” is not because of the Anti-tobacco crowd’s demands.

    I once watched as they released the pressure on a newly drilled “wellhead”…… and it “SCREAMED” so loud for like 15 to 18 minutes that one couldn’t hear themselves think …. and that was standing bout 100 yards away from it.

  92. Laws of Nature says:
    April 28, 2014 at 7:03 pm

    Beside the fact that anthropogenic influx into the ocean surface water is bigger that the “outgasing” at any given time, this reservoir could still be controlled and dominated by deep sea influx.

    There are several indications that the deep oceans – ocean surface exchanges are very limited: the density of the deeper layers is higher than at most of the surface, ocean currents which mix deep ocean waters and surface waters are very limited (polar sinks and coastal upwelling). Migration of CO2 between the mixed layer and the deeper oceans is very limited as diffusion of CO2 in (sea)water is extremely slow. Only biolife gives a dropout of ~6 GtC/year of organic and inorganic carbon into the deep.
    One example: the surface waters follow the drop in 13C/12C ratio of the atmosphere within 2-3 years, while there is no measurable change in the deep oceans, except at the downwelling places.

    My own estimate of the atmosphere – deep ocean CO2 exchanges was ~40 GtC/year, based on the “thinning” of the human “fingerprint” of fossil fuel burning. That is confirmed by the decrease in 14C/12C ratio from the 1950’s nuclear test spike.

    The simple global mass balance thus is:

    increase in the atmosphere = human emissions + natural input – natural output
    or
    4.5 GtC/year = 9 GtC/year(human) + 50 GtC/year (ocean surface) + 40 GtC/year (deep oceans) + 60 GtC/year (biosphere) – 50.5 GtC/year (ocean surface) – 43 GtC/year (deep oceans) – 61 GtC/year (biosphere).

    These figures are based on:
    – The 60 GtC in and out of biosphere exchanges are based on seasonal O2 and δ13C changes. The 1 GtC/year net uptake is based on the O2 balance and trend.
    – The 50 GtC in and out of the ocean surface is based on total CO2 changes over the seasons minus the changes attributed to the biosphere. The 0.5 GtC/year extra uptake in the ocean surface is based on the increase of CO2 in the atmosphere and the Revelle/buffer factor for seawater.
    – The 40 GtC in and out of the deep oceans is based on δ13C and δ14C changes. The difference of 3 GtC/year is the residual in mass balance (confirmed by “human fingerprints” at downwelling places).

    Does it matter if the in/out fluxes are overestimated or underestimated? Not at all. Even if the seasonal in/outflux of the biosphere was 120 GtC/season i.s.o. 60 GtC/season, That doesn’t change the balance: still 1 GtC/year extra is absorbed in the biopshere as net result.

    Does it matter if the in/out fluxes change year by year? Hardly, the measured variability in sink rate is only +/- 2 GtC around the trend over the years.

    Does it matter if the in/out fluxes increased over time, as Bart alleges? That may matter, but only if the sinks are extremely fast expanding together with the increase in natural supply and the natural supply/circulation increased in lockstep with human emissions. But there is not the slightest sign that the natural circulation increased over time, to the contrary it slightly decreased…

  93. Latitude says:
    April 29, 2014 at 8:55 am

    CH4 levels in the previous interglacial (the “Eemian”), were 700 ppbv. Temperatures in Alaska and Siberia 5-10°C higher than today, all permafrost melted and trees were growing up to the Arctic Ocean…
    We are currently at 1830 ppbv (see the carbon tracker at http://www.esrl.noaa.gov/gmd/dv/iadv/ for methane at Mauna Loa). It is easy to blame humans for the difference: one can see the curve in the Law Dome ice cores:

    Strange, a similar HS shape for CH4 as for CO2? Did the swamps suddenly release more CO2 since 1850? And why not in the warm(er) MWP?

  94. Samuel C Cogar says:
    April 29, 2014 at 11:26 am

    Ferdinand, are you trying to bedazzle me

    All I wanted to say is that the trend and the seasonal variation have different causes and different effects, which in this case are additive: because the CO2 trend is positive, the seasonal trend in the data will shift somewhat and the upgoing flank of the seasonal cycle will seem to be steeper than the downgoing one. I just tried to separate the seasonal effect from the trend…

    Really now, Ferdinand, and just how long does it take for the maximum emissions of surface emitted CO2 to reach the 3,400 m height of Mauna Loa? And is that the same amount of time that it takes before the minimum emissions of surface emitted CO2 is detected at the 3,400 m height of Mauna Loa?

    Here an already old (1960’s!) estimate of the shift in seasonal timing with height:

    But none of the above explains the steady and consistent 56 consecutive years of the bi-yearly cycling of CO2

    If you look into the graphs over a few years in detail, you will see that the seasonal cycle is not that steady for each year. In some years (1992 Pinatubo) the sinks dominate such that the residual CO2 increase in the atmosphere is very low. In other years (1998 El Niño) near all emissions remain in the atmosphere. Here a plot of 3 seasons, measured at 4 different stations:

    There may be a shift in seasonality and amplitude over the full 50+ years period of Mauna Loa, at least I have heard of an increase in seasonal amplitude, but I have no reference. But please go ahead with the calculations: the carbon tracker ( http://www.esrl.noaa.gov/gmd/dv/iadv/ ) gives you all the available data you want for all stations, including the 13C/12C ratio which shows the shift between uptake and release of CO2 by the biosphere…

    And if there has been such a change in the bi-yearly cycle then it can not be attributed to “human caused”

    As far as I know, I never said that humans do influence the seasonal cycle, all what they do is that their emissions cause the upgoing trend where the seasonal cycle lingers around. There may be a small indirect influence from a little warming caused by the extra human induced CO2, but in my opinion that is dwarfed by the natural variations…

  95. Ferdinand Engelbeen says some interesting stuff at: April 29, 2014 at 3:27 pm

    a- deep oceans – ocean surface exchanges are very limited
    My own estimate of the atmosphere – deep ocean CO2 exchanges was ~40 GtC/year, based on the “thinning” of the human “fingerprint” of fossil fuel burning. That is confirmed by the decrease in 14C/12C ratio from the 1950′s nuclear test spike.

    b- The simple global mass balance thus is:
    c- Does it matter if the in/out fluxes increased over time, as Bart alleges? That may matter, but only if the sinks are extremely fast

    Well your numbers used in a and b seem to be different than the “official” numbers:

    c- I dont think Bart necessarily implies that the anthropogenic increase drives any change in the deep ocean fluxes, just a change in time would be enough.
    The little ice age is over isnt it, that must affect the ocean currents as a change in temperature without any doubt changes the viscosity of the water among other parameters.

    And last not least, since none of your argument is really new, I can only repeat my critique on it until you are willing to address it:
    So, I guess we can agree that IF the fluxes on a global scale WERE not known with sufficient precision your statement WOULD have to be expanded over all [oceans].

    Your numbers are wildly different from the NOAA ones, their numbers are changing over the years.. that simply does not inspire confidence.. care to put uncertainty ranges to your numbers.. (especially when dealing with numbers from the 19th century as in the NOAA diagram)

  96. Laws of Nature says:
    April 29, 2014 at 6:03 pm

    A few remarks about the new(er) NOAA diagram:

    The ~120 GtC in and out of vegetation in general is split into 60 GtC in and out between (nightly) respiration and (daily) uptake during the growing season and isn’t reaching the bulk of the atmosphere. The other 60 GtC in and out is reaching the bulk of the atmosphere and can be measured in the 13C/12C change over the seasons in the bulk of the atmosphere like at Mauna Loa.

    The 40 GtC deep ocean – atmosphere exchange is the final result of the total deep ocean – ocean surface – atmosphere exchanges, in the NOAA diagram shown as going via the surface layer. But most of the change between atmosphere and deep oceans is simply bypassing the bulk (~90%) of the mixed layer via direct sinks and upwelling (~5% of the ocean surface each way).

    The 22.2 GtC out / 20 GtC in between atmosphere and ocean surface due to human influences doesn’t make sense, as human emissions or the increase of CO2 in the atmosphere doesn’t affect the carbon cycle in the oceans: there is abundant CO2 in the ocean surface, that is not a limiting factor for growth. I don’t see if and why the ~90 GtC cycle changed over time, except if they attribute all warming of the ocean’s surface to humans and the warming changed the ocean’s biocycle, but I have no figures for the influence of temperature on the ocean carbon cycle. Anyway, a 25% change in carbon cycle for an average change of less than 1 K in ocean temperature seems way out of reality.

    I dont think Bart necessarily implies that the anthropogenic increase drives any change in the deep ocean fluxes

    The theory of Bart is that a natural increase in carbon cycle drives the increase of CO2 in the atmosphere. That is only possible if there is a huge increase in input from the oceans or vegetation (all other sources too small or too slow) and the sinks are very fast reacting on the increase in input. Only in that case, human emissions will be dwarfed by the natural carbon cycle. The biosphere can be excluded, as there is very little change in the seasonal 13C/12C amplitude, but the oceans can be an expanding source if the deep ocean upwelling increased over time either in amount or concentration or both. But as said before, there is not the slightest sign that the natural carbon cycle increased in throughput and any substantial release from the oceans would increase the 13C/12C ratio in the atmosphere, while we see a firm drop…

    care to put uncertainty ranges to your numbers

    No problem with that. Year by year variability of fluxes and balances:
    – Any individual CO2 flux: -50 to +100%.
    – Overall balance of the biosphere: +/- 5%, based on changes of the 13C/12C ratio and the oxygen balance with temperature.
    – Overall balance of the oceans: +/- 3%, based on changes in pCO2 difference at the upwelling places. Downwelling places are less affected as the area of downwelling changes with temperature. The ocean’s mixed layer has a huge effect on the seasonal cycle, but a small effect on residual changes.
    – Overall balance in total: +/- 1.5%, based on the measured variability of the rate of change in the atmosphere:

    All what counts is the overall mass balance: even if every individual flux in any year changed -50 to +100% compared to the previous year. Only the overall balance is what gives a change of CO2 in the atmosphere.
    Temperature is the main driver for the year by year variability, but even so, the variability is very small compared to the huge in and out fluxes involved. Anyway, temperature is not the cause of the bulk of the increase of CO2 in the atmosphere…

  97. Dear Dr. Engelbeen,

    I have to admit that I cannot follow, how you get to the “The 40 GtC deep ocean – atmosphere exchange” from the NOAA numbers.

    As for your uncertainties, they are huge for the individual fluxes, but small for the sums, which seems mathematically wrong to me!
    However the important question here would be, how much of an undetected trend in the up/downwelling CO2 from the deep oceans is possible.. Your 3% seems low for these fluxes, as in increase of 3% in the mixed layer would give about 3% less up and 3%more downwelling CO2 without any room for other fluctuations.
    ” any substantial release from the oceans would increase the 13C/12C ratio in the atmosphere, while we see a firm drop…” is an incorrect statement, if the upwelling takes place on a planet with an anthropogenic source, just like Essenhigh showed years ago. Please read his, mine and Bart’s arguments on this and take them into account (and stop iterating this wrong statements).

    I think you post ideology based house numbers which are not very reliable.

    Ferdinand Engelbeen says:
    April 30, 2014 at 1:47 am
    “[..]Temperature is the main driver for the year by year variability, but even so, the variability is very small compared to the huge in and out fluxes involved.”
    What about ocean currents? Or vulcanic or bacterial activity? Algae bloom?

  98. Laws of Nature says:
    April 30, 2014 at 2:58 am

    The 40 GtC deep ocean – atmosphere exchange

    The NOAA graph only shows a 90 GtC in/out flux between atmosphere and ocean surface and the exchange with the deep oceans is indirectly via the surface. In reality, the exchange atmosphere – deep oceans is quite direct and largely bypasses the global surface layer. The 40 GtC in/out is based on the thinning of the δ13C and δ14C levels, as what goes into the deep oceans is the current isotopic composition, but what comes out is the composition of ~1000 years ago and influenced by the composition of the huge deep oceans reservoir.
    (BTW, no “Dr.”, have a B.Sc. in process chemistry, but specialised in chemical process automation).

    As for your uncertainties, they are huge for the individual fluxes, but small for the sums
    If one looks at the CO2 levels in a small area over land, that may show very large changes over one day, depending of wind and inversion. See e.g. a few days at Giessen, Germany, semi-rural, compared to the raw hourly data at Mauna Loa and the South Pole for the same days:

    The local change in flux over a day (and over the seasons) is enormous, but hardly influences the global CO2 levels when all individual fluxes are summed up and mixed into the bulk of the atmosphere.

    Your 3% seems low for these fluxes, as in increase of 3% in the mixed layer would give about 3% less up and 3%more downwelling CO2 without any room for other fluctuations.

    You need to make a differentiation between quantities, exchanges and net changes… If the CO2 level in the atmosphere changes with 30%, the outflux to the mixed layer will increase and the influx from the mixed layer will decrease because the pCO2 difference increases between the atmosphere and the mixed layer. That goes on until the pCO2 difference is zero (if ever). But that hardly influences the seasonal fluxes, as these are temperature dependent and only partially pressure (difference) dependent. Thus the temperature influence is largely independent of the CO2 levels in the different reservoirs while the net change over a full year is both pressure and temperature dependent. The temperature trend meanwhile over the past 160 years is very modest. Most of the temperature variation levels out over a few years.

    is an incorrect statement, if the upwelling takes place on a planet with an anthropogenic source

    Yes and no: There are only a few possibilities:
    The measured 13C/12C ratio is about 1/3rd of what can be expected if all human emissions would stay in the atmosphere. That means that either 2/3rd of the low-13CO2 is exchanged with high-13CO2 from the oceans without influencing the total amount in the atmosphere or the high-13CO2 from the oceans is additional.

    Humans add ~9 GtC/year low-13CO2 to the atmosphere. To compensate the 13C/12C ratio to what is measured, one need ~40 GtC high-13CO2 from the oceans:

    As the biosphere sinks some 1 GtC/year and the mixed layer sinks some 0.5 GtC/year and the increase in the atmosphere is around 4.5 GtC/year, the deep oceans (there are no other known fast sinks) should eat some 3 GtC/year away. Thus there is simply no room for any residual extra CO2 from the deep oceans. The thinning of the 13C/12C ratio thus is simple replacement and not addition.

    If Bart was right with his extra carbon circulation from the deep oceans, that MUST mimic the human emissions, because the sinks don’t make a differentiation between natural and human CO2 (except a very small one for the difference in isotopes). That means that the near tripling in human emissions and near tripling of sink speed over the period 1960-current should be caused by a near tripling in natural input/circulation. But as the biosphere and the mixed layer don’t add to that, only the deep oceans must have increased their throughput from ~40 GtC/year to ~290 GtC/year. The result of that increase on the 13C/12C ratio is the orange trend here:

    Which shows that the observed deep ocean throughput is rather constant and didn’t increase over the past 50 years. Neither is that the case for the 14C/12C bomb spike curve…

    What about ocean currents?

    Ocean currents like El Niño/ENSO are the main drivers of temperature variations and algal blooms. But these are included in the year-by-year variability, which is quite modest. Volcanic activity has little impact on CO2 levels: even de Pinatubo caused a (temperature related) dip in CO2 increase rate, not a spike…

  99. Ferdinand Engelbeen says:
    April 29, 2014 at 4:27 pm

    If you look into the (CO2) graphs over a few years in detail, you will see that the seasonal cycle is not that steady for each year. In some years (1992 Pinatubo) the sinks dominate such that the residual CO2 increase in the atmosphere is very low. In other years (1998 El Niño) near all emissions remain in the atmosphere.
    ———————-

    Ferdinand, me thinks you have picked out two (2) data “points”, (1992 Pinatubo & 1998 El Niño) and then assumed a direct relationship between them and the decrease/increase in atmospheric CO2 ppm relative to near surface air temperatures and atmosphe particulate in the 1st case …… and near surface air temperatures and increased ocean temperatures in the 2nd case.

    Now there might be a “correlation” therein between surface temperatures but I wouldn’t have a clue what it was because it does not remain consistent over a 34 year time frame (1979-2013). So, it is of my learned opinion that there is another factor that is the “primary” driver of the CO2 ppm increases …. and that the atmospheric conditions (temperature/particulate) are “iffy” factors that may or may not be relevant.

    Ferdinand, to resolve my suspicions on this matter …. I uploaded a copy of this temperature graph, to wit:

    1979-2013 UAH satellite global lower atmosphere temperatures

    And then I extracted this ppm data from, to wit:
    ftp://aftp.cmdl.noaa.gov/products/trends/co2/co2_mm_mlo.txt

    Maximum yearly ppm data

    year month CO2 ppm
    1979 6 1979.458 339.20
    1980 5 1980.375 341.47
    1981 5 1981.375 343.01
    1982 5 1982.375 344.67
    1983 5 1983.375 345.96
    1984 5 1984.375 347.55
    1985 5 1985.375 348.92
    1986 5 1986.375 350.53
    1987 5 1987.375 352.14
    1988 5 1988.375 354.18
    1989 5 1989.375 355.89
    1990 5 1990.375 357.29
    1991 5 1991.375 359.09
    1992 5 1992.375 359.55 Pinatubo
    1993 5 1993.375 360.19
    1994 5 1994.375 361.68
    1995 5 1995.375 363.77
    1996 5 1996.375 365.16
    1997 5 1997.375 366.69
    1998 5 1998.375 369.49 El Niño
    1999 4 1999.292 370.96
    2000 4 2000.292 371.82
    2001 5 2001.375 373.82
    2002 5 2002.375 375.65
    2003 5 2003.375 378.50
    2004 5 2004.375 380.63
    2005 5 2005.375 382.47
    2006 5 2006.375 384.98
    2007 5 2007.375 386.58
    2008 5 2008.375 388.50
    2009 5 2009.375 390.19
    2010 5 2010.375 393.04
    2011 5 2011.375 394.21
    2012 5 2012.375 396.78
    2013 5 2013.375 399.76

    And then I plotted the above ppm data on the above cited graph and the results was uploaded to this site, to wit:

    So, please tell me, Ferdinand, based on the above plotted graph, ….. what is the primary “driver” of atmospheric CO2 ppm? Surely not near-surface atmospheric temperatures.

  100. Samuel C Cogar says:
    April 30, 2014 at 8:39 am

    Now there might be a “correlation” therein between surface temperatures

    The correlation is between the temperature changes and the CO2 changes. Not with the trend. See Wood for Trees, where the CO2 changes lag the temperature changes. But that is only for the variability around the trend.

    The trend itself is almost completely caused by humans:

    and

  101. Ferdinand Engelbeen says:
    April 30, 2014 at 11:49 am
    —————————–

    Let’s see now, Ferdinand, in response to my question you are claiming …. correlations, changes, trends and variability.

    Why those thingys sound so scientifically that I could almost puke.

    Ya got any more “words of wisdom” for me?

    And I use to think I knew why the proponents of CAGW were winning the argument.

Comments are closed.