The Electric Oceanic Acid Test

Guest Post by Willis Eschenbach

I’m a long-time ocean devotee. I’ve spent a good chunk of my life on and under the ocean as a commercial and sport fisherman, a surfer, a blue-water sailor, and a commercial and sport diver. So I’m concerned that the new poster-boy of alarmism these days is sea-water “acidification” from CO2 dissolving into the ocean. Heck, even the name “acidification” is alarmist, because sea water is not acid, nor will it every be. What we are seeing is a slight reduction in how alkaline the sea water is.

There is a recent and interesting study in GRL by Byrne et al., entitled “Direct observations of basin-wide acidification of the North Pacific Ocean“. This study reports on the change in ocean alkalinity over a 15 year period (1991-2006) along a transect of the North Pacific from Hawaii to Alaska. (A “transect” is a path along which one measures some variable or variables.) Here is the path of the transect:

Figure 1. Path (transect) used for the measurement of the change in oceanic alkalinity.

I love researching climate, because there’s always so much to learn. Here’s what I learned from the Byrne et al. paper.

The first thing that I learned is that when you go from the tropics (Hawaii) to the North Pacific (Alaska), the water becomes less and less alkaline. Who knew? So even without any CO2, if you want to experience “acidification” of the ocean water, just go from Hawaii to Alaska … you didn’t notice the change from the “acidification”? You didn’t have your toenails dissolved by the increased acidity?

Well, the sea creatures didn’t notice either. They flourish in both the more alkaline Hawaiian waters and the less alkaline Alaskan waters. So let’s take a look at how large the change is along the transect.

Changes in alkalinity/acidity are measured in units called “pH”. A neutral solution has a pH of 7.0. Above a pH of 7.0, the solution is alkaline. A solution with a pH less than 7.0 is acidic. pH is a logarithmic scale, so a solution with a pH of 9.0 is ten times as alkaline as a solution with a pH of 8.0.

Figure 2 shows the measured pH along the transect. The full size graphic is here.

Figure 2. Measured ocean pH from the surface down to the ocean bottom along the transect shown in Figure 1.

The second thing I learned from the study is that the pH of the ocean is very different in different locations. As one goes from Hawaii to Alaska the pH slowly decreases along the transect, dropping from 8.05 all the way down to 7.65. This is a change in pH of almost half a unit. And everywhere along the transect, the water at depth is much less alkaline, with a minimum value of about 7.25.

The third thing I learned from the study is how little humans have changed the pH of the ocean. Figure 3 shows their graph of the anthropogenic pH changes along the transect. The full-sized graphic is here:

Figure 3. Anthropogenic changes in the pH, from the surface to 1,000 metres depth, over 15 years (1991-2006)

The area of the greatest anthropogenic change over the fifteen years of the study, as one might imagine, is at the surface. The maximum anthropogenic change over the entire transect was -0.03 pH in fifteen years. The average anthropogenic change over the top 150 metre depth was -0.023. From there down to 800 metres the average anthropogenic change was -0.011 in fifteen years.

This means that for the top 800 metres of the ocean, where the majority of the oceanic life exists, the human induced change in pH was -0.013 over 15 years. This was also about the amount of pH change in the waters around Hawaii.

Now, remember that the difference in pH between the surface water in Hawaii and Alaskan is 0.50 pH units. That means that at the current rate of change, the surface water in Hawaii will be as alkaline as the current Alaskan surface water in … well … um … lessee, divide by eleventeen, carry the quadratic residual … I get a figure of 566 years.

But of course, that is assuming that there would not be any mixing of the water during that half-millennium. The ocean is a huge place, containing a vast amount of carbon. The atmosphere contains about 750 gigatonnes of carbon in the form of CO2. The ocean contains about fifty times that amount. It is slowly mixed by wind, wave, and currents. As a result, the human carbon contribution will not stay in the upper layers as shown in the graphs above. It will be mixed into the deeper layers. Some will go into the sediments. Some will precipitate out of solution. So even in 500 years, Hawaiian waters are very unlikely to have the alkalinity of Alaskan waters.

The final thing I learned from this study is that creatures in the ocean live happily in a wide range of alkalinities, from a high of over 8.0 down to almost neutral. As a result, the idea that a slight change in alkalinity will somehow knock the ocean dead doesn’t make any sense. By geological standards, the CO2 concentration in the atmosphere is currently quite low. It has been several times higher in the past, with the inevitable changes in the oceanic pH … and despite that, the life in the ocean continued to flourish.

My conclusion? To mis-quote Mark Twain, “The reports of the ocean’s death have been greatly exaggerated.”

[UPDATE] Several people have asked how I know that their method for separating the amount of anthropogenic warming from the total warming is correct. I do not know if it is correct. I have assumed it is for the purposes of this discussion, to show that even if they are correct, the amount is so small and the effect would be so slow as to be meaningless.

[UPDATE] WUWT regular Smokey pointed us to a very interesting dataset. It shows the monthly changes in pH at the inlet pipe to the world famous Monterey Bay Aquarium in central California. I used to fish commercially for squid just offshore of the aquarium, it is a lovely sight at night. Figure 4 shows the pH record for the inlet water.

Figure 4. pH measurements at the inlet pipe to the Monterey Bay Aquarium. Inlet depth is 50′ (15 metres). Light yellow lines show standard error of each month’s measurements, indicating a wide spread of pH values in each month. Red interval at the top right shows the theoretical pH change which the Byrne et al. paper says would have occurred over the time period of the dataset. Photo shows kids at the Aquarium looking at the fish. Photo source.

There are several conclusions from this. First, the sea creatures in the Monterey Bay can easily withstand a change in pH of 0.5 in the course of a single month. Second, the Byrne estimate of the theoretical change from anthropogenic CO2 over the period (red interval, upper right corner) is so tiny as to be totally lost in the noise.

This ability to withstand changes in the pH is also visible in the coral atolls. It is not widely recognized that the pH of the sea water is affected by the net production of carbon by the life processes of the coral reefs. This makes the water on the reef less alkaline (more acidic) than the surrounding ocean water. Obviously, all of the lagoon life thrives in that more acidic water.

In addition, because of the combination of the production of carbon by the reef and the changes in the amount of water entering the lagoon with the tides, the pH of the water can change quite rapidly. For example, in a study done in Shiraho Reef, the pH of the water inside the reef changes in 12 hours by one full pH unit (7.8 to 8.8). This represents about a thousand years worth of the theoretical anthropogenic change estimated from the Byrne et al. paper …

The sea is a complex, buffered environment in which the pH is changing constantly. The life there is able to live and thrive despite rapidly large variations in pH. I’m sorry, but I see no reason to be concerned about possible theoretical damage from a possible theoretical change in oceanic pH from increasing CO2.

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252 thoughts on “The Electric Oceanic Acid Test

  1. How exactly did humans cause pH to increase at about 1000 meters between 25 degrees North latitude and 30 degrees North latitude? This “human induced change”-is it really just a difference of the beginning of trend lines and the end? Which basically assumes that the only way the ocean’s pH can change, even in individual locations, is because of people. That strikes me as ridiculous.

  2. Given how little we know about what is the real human contribution to atmospheric CO2, I find it incredible that the authors can begin to discuss a pH change attributable to human activity. They MUST be expressing an opinion or speculation here as they have no definitive means of determining a human influence.

    As the equilibrium of bicarbonate/carbonate and carbonate and calcium ions/calcium carbonate is temperature dependent and complicated by the lower solubility of calcium carbonate in warm water versus cold, this is a more complicated system than is presented here. The two equilibrium would work against each other in response to temperature changes.

    Thus, a wonderful observation of the oceans as a system about which we still have much to learn, but a meaningless discussion of human effects.

  3. interesting. i didn’t read the paper but how do we assume any ‘human inducement’? but i get the point.

  4. Not related, but I just saw this note on the BBC.

    http://news.bbc.co.uk/2/hi/science_and_environment/10342318.stm

    I don’t know whether to laugh or cry. I will say that I am making an effort to read the entire and very well written ” Global Warming Advocacy Science: a Cross Examination” by Jason Scott Johnston, U of Penn, May 2010, uploaded to this site a few days ago.

    As the rain blasts start to pummel my house….I bid you a warm good evening.

  5. The polynesians used to navigate by (among other things) tasting the sea water. I had assumed that they were tasting for salinity or for microbial life; could they have been tasting for alkalinity too?

  6. And the *same* sea creatures flourish in both Hawaii and Alaska? Without any adaptation that might take a few million years? And our emissions aren’t currently accelerating?

    timetochooseagain: the paper explains how they distinguished natural changes from anthropogenic changes. Natural variability is shown in the paper’s figure 3. The scale is greater than the anthropogenic variation (figure 4), but note that natural variability will add up to zero over longer time scales, anthropogenic variability will not.

  7. This is what you would expect from Henry’s law and the temperature gradient between Hawaii and Alaska. The difference at depth is almost certainly driven by the vertical temperature gradient.

  8. Hey! Chemistry! My field. Awesome.

    First, when CO2 dissolves in water, you get carbonic acid.

    CO2 + H2O –> H2CO3

    The dissolved gas concentrations are higher in colder water and higher pressures, which explains the pH closer to 7.0. This is counter-intuitive, as people think warmer solutions dissolve more stuff (which they do). But if you heat up any liquid, like a pot of water on the stove, you start seeing bubbles. That’s dissolved gas escaping as the temperature increases. So, in warmer waters, there’s less dissolved CO2, so the pH will be higher as there’s less carbonic acid.

    So this “acidification of the oceans” meme is rather odd. As the global temperature increases, so does the surface ocean temperature. And when that happens, the surface can hold less CO2, which means it’s not going to be as acidic. I see the system as self regulating and something not to worry about.

  9. Excellent post.
    Provides a real informational increment and helps put the ocean acidification claims into perspective.
    It would be interesting to have some explanation as to why the ocean is alkaline in the first place, as the inputs from the atmosphere, including CO2 as well as nitric oxydes from lightning are acidic.
    Is the biological input in the tropics providing the alkalinity observed?

  10. Now what if a subsea volcano or vent was slowly releasing gases and other materials?. Would it release sulfates, carbon dioxide or other pH modifiers? How would one separate that background level from the anthropogenic?

  11. Joel,

    Has it occurred to you that mankind has already burned a significant percentage of all the fossil fuels available to mankind, and our contribution to ocean alkalinity is insignificant. Over the course of the next 400 years any effects caused by mankinds C02 emissions will peak and fade away without causing ANY affects upon sea life.

  12. By geological standards, the CO2 concentration in the atmosphere is currently quite low. It has been several times higher in the past, with the inevitable changes in the oceanic pH … and despite that, the life in the ocean continued to flourish.


    This is how I look at claims of “unprecedented” rise in [....insert climate claim...]. Whenever you look back in time we know we have had higher c02 levels than present, we know we have had higher global mean temperatures than the present and yet no runaway boiling of the planet. We are still here!

    Acid Test
    Are oceans becoming more acidic and is this a threat to marine life?
    Biological Effects of "Ocean Acidification"
    In CO2-rich Environment, Some Ocean Dwellers Increase Shell Production
    Phytoplankton Calcification in a High-CO2 World
    Modern-age buildup of CO2 and its effects on seawater acidity and salinity
    “This paper’s results concerning average seawater salinity and acidity show that, on a global scale and over the time scales considered (hundreds of years), there would not be accentuated changes in either seawater salinity or acidity from the observed or hypothesized rises in atmospheric CO2 concentrations. ”

    And finally here is a blogger’s view of the new scare or in other words funding opportunity. :o)

  13. DocattheAutopsy,
    If I’ve got this straight, points in the ocean that are acidifying must be cooling?

  14. The relationship betweern pH and alkalinity is not straight forward because of the buffering effect of carbon dioxide/carbonate/bicarbonate ions in water as could be shown when a carbonate solution is titrated. There is more photosynthesis at the warmer surface water closer to the tropics that removes the carbon dioxide from the water and also carbon dioxide is less soluble. As the water pressure increases, there is more dissolved carbo dioxide. As corals are made mostly of calcium carbonate, people often think corals reduces the carbon dioxide in seawater. However, for every calcium ions there are two ions of bicarbonate. To form one molecule of calcium carbonate, one morelcule of carbon dioxide is added by the coral to the seawater.

  15. By observing one fourth of an approximate 60 year ocean atmosphere oscillation they know all there is to know about the ocean PH balance. WOW! How much has it changed naturally over the last 10,000 years or even the last 800,000 years? I wonder what the human population along that transect of the ocean?

  16. “‘DocattheAutopsy says:
    And when that happens, the surface can hold less CO2, which means it’s not going to be as acidic””

    and they claim that the slight warming right now, at our present CO2 levels, is causing the ocean to release CO2.
    But at even higher CO2 levels, with even more warming, the ocean is supposed to somehow take up and hold more CO2 – making it less alkaline.

    Just checked the pH in my front yard, I live on a rock in the middle of the Caribbean, it’s 8.4 Haven’t noticed any sea rise either.

  17. Two linked papers from New Zealand take some account of the ocean as a host for biota. I have read but not studied these, but on a quick read I cannot see any immediate objections, except to the pronunciation of “fish and chips.”

    My Internet search was for terms including titration of ocean water with CO2 and pH change. There are other interesting papers. Not many deal with direct electrode pH measurement and titration with CO2, which one would have thought to be the essential starting point of any investigation of the broader topic.

    http://www.seafriends.org.nz/issues/global/acid.htm

    http://www.seafriends.org.nz/issues/global/acid2.htm

    These papers give some answers to some questions above. Well worth a study. See especially the annual variation in the second paper under “BATS” from the Bermuda area, bottom graph for pH.

  18. “”Joel says:””

    Joel, rains, wind, storms, tides, upwellings, El Nino/La Nina, etc can cause very rapid, almost instant, changes in pH, salinity, temperature, Ca and carbonate levels, etc etc

    Everything out there has evolved to deal with that, nothing out there is that delicate.

    They ship corals all over the world in plastic fish bags, acclimate them to a holding facility, acclimate them to shipping water, acclimate them to a new warehouse, acclimate them again to a new pet shop, acclimate them again to someone’s aquarium. And all along the way their pH go up and down and all over the place.

  19. DocattheAutopsy says:
    June 19, 2010 at 6:40 pm
    Hey! Chemistry! My field. Awesome……….
    So this “acidification of the oceans” meme is rather odd. As the global temperature increases, so does the surface ocean temperature. And when that happens, the surface can hold less CO2, which means it’s not going to be as acidic. I see the system as self regulating and something not to worry about.

    However you’ve forgotten that the equilibrium concentration of CO2 in the surface water is also dependent on the pCO2 in the atmosphere which is being steadily increased by fossil fuel combustion.

  20. Robert M,

    ah, a Peak Oil fan … we haven’t even scratched the surface of the fossil fuels available to us around the globe. Have you noticed that there have been huge, HUGE oil and natural gas discoveries in the last year …. everytime we really look we find more … we have 200-300 years of coal in the US alone …

    since we could burn it all and still not effect global temperatures I’m not really worried …

  21. A couple of questions for our alarmist friends:

    1) What is the ultimate carrying capacity of an infinitely buffered alkaline solution for an acid gas?

    2) Where does limestone come from?

  22. I’m ready for a solar eruption (because I believe what NASA tells me). How will that affect ocean pH? :)

    Too much speculation?

  23. Phil. says:

    “However you’ve forgotten that the equilibrium concentration of CO2 in the surface water is also dependent on the pCO2 in the atmosphere which is being steadily increased by fossil fuel combustion.”

    Even if true, that is bad, because …?

  24. Excellent post apart from the assumption, without any form of justification, that humans have induced a pH change.

  25. Joel-The changes still seem odd to me. If you don’t have the answer, does anyone else have a plausible explanation for why there is an increase of pH with time at a depth of 1000 meters between 25 N and 30 N? And another question, this one specifically for you Joel: What do you consider “longer timescales”? Centuries? Millennia? Millions even billions of years? And do you believe that Nature is static over that timescale? Because it isn’t over any timescale. Even over billions of years, the Sun gets brighter and eventually expands to engulf us, later sloughing off it’s outer layers in a huge explosion and becoming a dim white dwarf. I’m not trying to make a point, it’s just that I don’t really think that “natural variability will average out to zero” is something that can be said to be accurate. On the other hand, anthropogenic effects will amount to zero in billions of years. Am I being pedantic? Yes. But that’s the way I am.

  26. Joel says:
    June 19, 2010 at 6:26 pm

    “…but note that natural variability will add up to zero over longer time scales, anthropogenic variability will not.”

    Is this one of those untrue statements that has no real meaning and is only designed to frighten? Yes…I believe it is!

    Nothing in nature is ‘sustainable’ if one considers long enough time periods. Nothing in nature is ‘balanced’ unless one considers only very short time periods, and even that is a stretch. The nature of Nature is change. Get use to it. The rest of nature has no problem with it, only semi-educated, wealthy Westerners seem to think the world is ‘broken’ if it is not the way it was when they were young.

  27. And they wonder why AGW credibility is going down the drain so quickly.
    Endless streams of nebulous claims (like ocean acidification) will do that.
    Right up there with the 10 foot sea-level rise currently lapping the steps of Capitol Hill.

  28. The final thing I learned from this study is that creatures in the ocean live happily in a wide range of alkalinities, from a high of over 8.0 down to almost neutral. As a result, the idea that a slight change in alkalinity will somehow knock the ocean dead doesn’t make any sense. By geological standards, the CO2 concentration in the atmosphere is currently quite low. It has been several times higher in the past, with the inevitable changes in the oceanic pH … and despite that, the life in the ocean continued to flourish.

    But not the same life!
    Case in point, the PETM mass extinction involved a jump in CO2 and temperature and an associated extinction of about 95% of marine lifeforms. It took ~80,000 years for the oceanic chemistry to stabilize.

  29. “By geological standards, the CO2 concentration in the atmosphere is currently quite low. It has been several times higher in the past…”

    Added CO2 at the surface (from the atmosphere) should be making the surface water less alkaline than successively deeper waters, but the charts show just the opposite. So, with deeper water being less alkaline than surface water, doesn’t that imply that CO2 is coming out of the ocean and into the atmosphere? Geologically low levels of atmospheric CO2 are “sucking” the CO2 out of the water (pardon the lack of scientific jargon here.)

    Isn’t this what we would expect? First temperatures rise, and then CO2 goes up, in this case from the ocean. Isn’t this paper yet another disproof that rising atmospheric CO2 causes rising temperatures?

  30. An amazing claim from this paper:
    “The component of pH change associated with penetration of anthropogenic CO2 into the upper ocean (ΔpHant, Figure 4) is given by the difference between total pH change (Figure 2) and the pH change attributable to variations in respiration and ocean ventilation (Figure 3). Evidence of anthropogenic influence is seen to depths of 150 m along the entire section. In this zone, ΔpHant varies between −0.01 and −0.03 with a mean value of −0.023 (±0.001). Between 22° and 38°N, anthropogenic acidification extends to more than 500 m and the −0.02 contour extends to more than 400 m.”

    What they are saying is they precisely know the oceanic ventilation and respiration pH effects and how these mechanism change along their transect (plus the data set and instrument corrections) such that they can confidently calculate a 0.023 pH decline from AGW CO2 in some regions. Who knew we had such command of oceanic ventilation and respiration?

  31. As someone who has also spent most of his life on, near or in the ocean- my great concern is that ocean acidification will hijack the very real problems we have with our keystone oyster populations. Oysters populations have collapsed as the result of physical habitat alteration (due to harvest) and importantly two devastating diseases Dermo and MSX. To give some idea how important oysters are in coastal ecosystems it is thought that prior to the collapse oysters filtered the entire contents of the Chesapeake every 3 days. Despite their keystone status the resources available to address this problem have been paltry at best. (Oysters and disease just don’t make good copy, fund raising or law suits.) Now the oysters will have to find a way to survive the new dictate that all shellfish problems must be caused by CO2.

  32. Complaining about calling a drop in alkalinity acidification is kind of silly. What else would you call it? You might as well complain that a drop in temperature from 100 degrees to 99 should not be called cooling.
    You cannot argue that the organisms will cope in general because there are already organisms coping with 7.25. These are at different latitudes, so unlikely to be the same species. Likely the equatorial species could cope given long enough to evolve, but we don’t know how long that requires. And the species at higher latitudes will be exposed to acidities for which there are no extant marine precedents.
    As for the back-of-the-envelope calculation about timescales of further acidification, it is contradicted by several more painstaking estimates: http://en.wikipedia.org/wiki/Ocean_acidification#Acidification. This is probably a lot to do with the fact that you have not taken into account that the CO2 level in the atmosphere is higher than at any time for a couple of hundred years, so the rate of acidification is higher than at any time in that period too – and increasing.
    Sorry – not up to your usual standard.

  33. The deep ocean (below 1,000 m) holds the largest amount of carbon dioxide than any other planet earth compartment – more then all the atmosphere (by orders of magnitude), more then all terrestrial carbon, more then all the fossil fuel burnt and more then all known fossil fuel reserves in the world. Even the IPCC reports agree with this. If you want to get very afraid, then the end is near if ever the deep ocean water masses erupt to the surface. Indeed, some published papers suggest this may have happened in the ancient past and caused massive changes to the earth. Basically the deep sea is under enormous pressure and very cold – water can hold much much more dissolve gas at pressure and when cold. So when the deep sea upwells to the surface it is like opening a bottle of carbonated drink – under pressure and in the fridge. There are many areas of the earth’s ocean that degass carbon dioxide to the atmosphere. It will probably prove that the concerns about ocean ‘acidification’ will be vastly exaggerated but it is a cause that is at least worth a look. Without question, some of the increased concentration of carbon dioxide in the air goes into solution in water, with >70 of the surface with an gas:water interface, some, of course, will dissolve into the water. So far the scientific jury is still very much out on the issue – so far some evidence for and some against for the jury. If a betting man, it will prove a very minor issue with respect to all the other problems that face the planet.

  34. Phil.: June 19, 2010 at 7:53 pm
    But not the same life!  Case in point, the PETM mass extinction involved a jump in CO2 and temperature and an associated extinction of about 95% of marine lifeforms. It took ~80,000 years for the oceanic chemistry to stabilize.

    “Stock check in Aisle 4, please. Supply of Depends getting low.”

    /dr.bill

  35. A mere -0.02 ph? But these are just alarmist “scientists”. Maybe some of the readers here might want to get a first hand experience of what a real scientist is actual like, that way they can spot these “alarmist climatologists” a mile away too:

    Just sat through 4 – 1½ hour lectures by one of my favorites, late Dr. Richard Feynman, on his quantum-electrodynamics (QED) theory, explained in exquisite detail with only chalk in a manner that anyone half knowledgeable in basic physics and algebra can follow. Staying away from complex numbers and mind twisting mathematics he lays out the theory and many examples only using simple pointers (vectors) and logic.

    Those more knowledgeable will recognize that his simple pointers and simple add and multiply operations are actually describing the complex number underlying this theory though he never fesses up to this until late in the series. So even the more experienced can get some deep insight too by using some upward mental translation.

    I have never seen a lecture given in such clarity, brilliant and so full of humility with a sprinkle of skeptism, but above all, he lets the data and logic guide him always.

    Also this is a great view of who Isaac Newton really was and how he thought.

    Richard Feynman describing the QED theory of “nearly everything”

    http://www.vega.org.uk/video/subseries/8

    If you like science and physics, this one is guaranteed to please!

  36. One other thing to consider: what is the standard error of their equipment? I’d be astounded if their measurement device was accurate below 0.01 pH Units. Their measurements only go to 3 sig figs, so a difference of even 0.03 pH over 15 years is pretty much zero to no change considering error.

  37. Willis- Thanks for another interesting post. It once again shows the paucity of ocean pH data available for analysis. I wonder if anyone would be successful at publishing a paper that compared two satellite sweeps on March 15, separated by 15 years (say 1995 and 2010), measured along a single 5 degree wide longitudinal stripe that only includes some of the Northern hemisphere, and drawing any sort of conclusion about anthropogenic influences (or lack thereof) on lower tropospheric temperatures.

    I find it remarkable that a climate science paper can claim, without resorting to a database of at least 50 years of observational pH data sampled at least 4 times per year and with some (any) spatial coverage, draw the conclusion that anthropogenic emissions of CO2 are responsible for a 0.01 – 0.02 pH change over a 15 year period. It is remarkably sad.

  38. “pH slowly decreases along the transect, dropping from 8.05 all the way down to 7.65. This is a change in pH of 0.5.”

    Isn’t this a change in pH of 0.4?

  39. This is probably a lot to do with the fact that you have not taken into account that the CO2 level in the atmosphere is higher than at any time for a couple of hundred years

    Not really. CO2 concentration is increasing more or less arithmetically, whereas pH is a logarithmic scale. So if CO2 concentration were the only factor in ocean pH, CO2 would have to increase by 10 times to give a pH increase of 1.

    But, as others have pointed out, increasing temperature acts to decrease the solubility of CO2. Increasing CO2 concentrations will also likely increase carbonate shell drop out by organisms. So we will really have to get cracking with CO2 production to affect the oceans by partial pressure of the gas.

    Humans may yet kill everything in the sea by over-fishing and pollution. Those are major concerns to me. CO2 acidification is an unnecessary distraction from the real issues.

    Complaining about calling a drop in alkalinity acidification is kind of silly.

    I beg to differ. It sets up the assumption in the mind of many that read it that the oceans were neutral and are rapidly being acidified. We here know that is wrong, but it is the obvious reading to a scientifically ignorant person. It raises the scare content.

    It is similar to the description of the “warm” temperatures in the Arctic. If you don’t read too deeply you get the impression that the temperatures are above freezing.

    Politicians are routinely rubbished for using excessively scary language where a technical person (economist, say) might use guarded terms. So it should be in climate science. Use the right terms and avoid the emotive rubbish.

  40. Derek B: June 19, 2010 at 8:29 pm
    Complaining about calling a drop in alkalinity acidification is kind of silly. What else would you call it? You might as well complain that a drop in temperature from 100 degrees to 99 should not be called cooling.

    In a Chemistry lab, it would be called ‘neutralization’ (like distilled water).
    Temperature doesn’t have any kind of identifiable ‘set point’ like that.
    And you know just as well as I do, that this is just alarmist rhetoric.

    /dr.bill

  41. Thanks, Willis, here’s a dissenting viewpoint from our friends in France:

    http://www.up.ethz.ch/education/biogeochem_cycles/reading_list/orr_nat_05.pdf

    I’ve personally long been concerned about the chemical nature of fossil fuel production, especially in terms of mercury and radionuclide emissions from coal plants. I tend to give acidification more credence than any problems due to warming.

    Then again, I’m but a humble biologist, drifting in a warm sea of discontent….

    BTW, Happy Father’s Day to you dads out there!

  42. So if we were to raise CO2 enough to make the ocean ten times as acidic as it is now, aside from being unable to breathe, we would be as acidic as mother’s milk and maple syrup. Something to think about.

  43. flyfisher says:
    June 19, 2010 at 8:53 pm
    One other thing to consider: what is the standard error of their equipment? I’d be astounded if their measurement device was accurate below 0.01 pH Units.

    Perhaps you should have read the paper (specifically Data and Methods):

    “Measurement precision on both transects was on the order of ±0.001″

  44. Any scientist that uses the term “Acidification” to describe changes in the ocean ph above 7.0 really needs to go back to kindy and start over again.

  45. Flyfisher:
    They are using spectrophotometric pH measurement and claim a precision of 0.001 pH units. Byrne, the cited study’s author, also holds several patents on the system and method for spectrophotometric pH measurement.
    I agree with you- any of the more conventional pH measurements methods would suffer significant drift in a large scale field application (at best +/- 0.02)
    Anyone with any info on whether this equipment actually performs in the field as claimed?

  46. I found this:

    http://oceanacidification.wordpress.com/2009/07/05/consequences-of-high-co2-and-ocean-acidification-for-microbes-in-the-global-ocean/

    “It was the view of the experts that experimental approaches should rely heavily on existing environments where higher CO2 and lower pH occurs naturally, such as zones of high respiration, particularly where respiration is much higher than primary production, and in cold polar seas, which have lower calcium carbonate saturation state. Freshwater lakes and estuarine waters offer exceptional opportunities since they are less well buffered than the oceans and experience daily to seasonal changes in hydrogen ion concentration that can be orders of magnitude greater than those projected for the oceans in the next century. Coastal and estuarine environments also experience substantial pH variations over short time and space scales. An important question is whether marine microbes have lost the metabolic flexibility of their freshwater counterparts because they have experienced relatively constant pH for 20 million years.”

  47. A thought – aquariums (the large public kind, not living-room sized) often have displays of tropical fish and corals. These are often in areas of colder (less alkaline) water (e.g. Seattle Aquarium). Presumably these use local seawater, filtered and heated, which may change the pH. While such large tanks are hardly natural ecosystems, corals don’t seem to ‘struggle’ in such environments. OK, perhaps they carefully control the pH and pCO2. Can anyone provide an insight?

  48. Smokey says:
    June 19, 2010 at 6:02 pm

    pH varies all over the place locally, too. [scroll down for charts]

    Sweet, Smokey, I love data. This is an excellent dataset, because it is from the Monterrey Bay Aquarium inlet pipe. I love the place, I used to fish squid commercially right offshore from the aquarium.

    I have posted the information as an [UPDATE] at the end of the head post. Take a look.

    Thanks again,

    w.

  49. Joel says:
    June 19, 2010 at 6:26 pm

    And the *same* sea creatures flourish in both Hawaii and Alaska? Without any adaptation that might take a few million years? And our emissions aren’t currently accelerating?

    Good questions, Joel. A number of sea creatures are wide ranging, with tuna being the champions, wandering all over the Pacific from the tropics to the far north. In addition, see my update at the end of the head post. Even creatures that live in one place regularly see changes of the same magnitude as the Hawaii-Alaska difference. Next, most sea creatures have fairly short lifespans, and thus can adapt in much less than a million years. Finally, the ocean is always changing, and as a result oceanic creatures are used to those rapid changes.

  50. pH of water in Danube river oscillates during the year between 7.9-8.5 and life just go on. Are there any pH proxies for ancient times? You know, when the bad CO2 was at 6,000ppm, runaway warming killed all life and oceans turned to dead acid marshes.

  51. Derek B says:
    June 19, 2010 at 8:29 pm

    Complaining about calling a drop in alkalinity acidification is kind of silly. What else would you call it? You might as well complain that a drop in temperature from 100 degrees to 99 should not be called cooling.

    I’d call it a drop in alkalinity …

    The term “acid” is reserved for solutions under a pH of 7. Would you call a chance from a pH of 3 to a pH of 4 “alkalinization”? The point is that the term is alarmist, because people who don’t know better will think that the ocean is going to be acidic. It is not.

    You cannot argue that the organisms will cope in general because there are already organisms coping with 7.25. These are at different latitudes, so unlikely to be the same species. Likely the equatorial species could cope given long enough to evolve, but we don’t know how long that requires. And the species at higher latitudes will be exposed to acidities for which there are no extant marine precedents.

    Not true. See my [UPDATE] at the end of the original post.

    As for the back-of-the-envelope calculation about timescales of further acidification, it is contradicted by several more painstaking estimates: http://en.wikipedia.org/wiki/Ocean_acidification#Acidification. This is probably a lot to do with the fact that you have not taken into account that the CO2 level in the atmosphere is higher than at any time for a couple of hundred years, so the rate of acidification is higher than at any time in that period too – and increasing.
    Sorry – not up to your usual standard.

    Back of the envelope calculations? The numbers that you refer us to are estimates. My numbers are based on actual measurements, one of the first large-scale measurements of the changes in oceanic pH. If you don’t like the numbers, don’t complain to me. Write to the guys who made the measurements. The rate of reduction of the alkalinity of the oceans is what it is measured to be, no matter what the atmosphere is doing.

  52. Derek B says:
    June 19, 2010 at 8:29 pm

    You cannot argue that the organisms will cope in general because there are already organisms coping with 7.25. These are at different latitudes, so unlikely to be the same species. Likely the equatorial species could cope given long enough to evolve, but we don’t know how long that requires. And the species at higher latitudes will be exposed to acidities for which there are no extant marine precedents.

    We should also consider the natural variations in ocean ph from hour to hour, tide to tide and day to day.
    Some of the most productive areas of the oceans are the upwelling zones (nutrients rise with the upwelling) these zones contain some of the most diverse and abundant species of all. These zones are also substantially less alkaline and the ph fluctuates greatly.
    Areas at and around river outflows are also abundant with species and organisms. The ph levels of these areas vary relatively substantially from tide to tide and river discharge highs to lows.

    In short, we shouldn’t sell “short” the resilience of the planets species. Just because WWF and Greenpeace say “delicate” and “finely balanced”, doesn’t make it so.

  53. Mike Hall says:
    June 19, 2010 at 8:34 pm

    The deep ocean (below 1,000 m) holds the largest amount of carbon dioxide than any other planet earth compartment – more then all the atmosphere (by orders of magnitude), more then all terrestrial carbon, more then all the fossil fuel burnt and more then all known fossil fuel reserves in the world. Even the IPCC reports agree with this. If you want to get very afraid, then the end is near if ever the deep ocean water masses erupt to the surface. Indeed, some published papers suggest this may have happened in the ancient past and caused massive changes to the earth. Basically the deep sea is under enormous pressure and very cold – water can hold much much more dissolve gas at pressure and when cold. So when the deep sea upwells to the surface it is like opening a bottle of carbonated drink – under pressure and in the fridge. There are many areas of the earth’s ocean that degass carbon dioxide to the atmosphere. It will probably prove that the concerns about ocean ‘acidification’ will be vastly exaggerated but it is a cause that is at least worth a look.

    Deep ocean water is coming to the surface constantly. It is called “upwelling”, and it is happening all over the planet. Sure, if the ocean were to flip like a pancake tomorrow so all the bottom water came to the top at once, we’d freeze our coconuts if we went swimming in Hawaii … but the thought of that happening doesn’t keep me up at night.

  54. Peter says:
    June 19, 2010 at 9:19 pm

    “pH slowly decreases along the transect, dropping from 8.05 all the way down to 7.65. This is a change in pH of 0.5.”

    Isn’t this a change in pH of 0.4?

    Thanks, fixed. Running too fast.

  55. Something I’ve not seen discussed in these studies of “Ocean Acidification” are the human emissions of far more potent acidifying gases – especially SO2 and NOx.

    This absence is puzzling, since these emissions were politically controversial in the ’70s and ’80s, with places like Sweden complaining loudly about acid rainfall with a pH of ~4, largely caused in those days by coal burning in the industrial countries of Europe. While Europe may have cleaned up its act somewhat, the rise of the Asian economies has ensured that global levels of SO2 emissions are still around the 150M metric tons per annum level. (See http://earthtrends.wri.org/searchable_db/results.php?years=all&variable_ID=812&theme=3&country_ID=all&country_classification_ID=all) NOx emissions seem to be increasing, also.

    Much of these emissions eventually ends up in the oceans. Might not this have a measureable impact on the oceanic pH? Surely this needs to be considered when studying ocean acidification?

  56. “Figure 3. Anthropogenic changes in the pH, from the surface to 1,000 metres depth, over 15 years (1991-2006)”

    And the proof for this statement is where exactly???

    Just because something changes in the environment, it doesn’t mean the cause is anthropogenic.

  57. As usual an interesting post Willis.
    As to the depth vs. pH question, could relate simply to the change in CO2 solubility with pressure and temperature?

  58. I just compared the monthly changes in pH at the inlet pipe to the Monterey Bay Aquarium to the HADcru global temperature record. An uncannily good match.

    It loks like the release of co2 from the top layer of the ocean tracks the variation in temperature very accurately and quickly.

    Thanks for a great post Willis.

  59. I am speculating here but would not the ‘melting’ freshwater ice caps and glaciers end up in the oceans thus dilluting the water as well. What would the net effect be?

  60. M White says:
    June 20, 2010 at 12:59 am

    “Figure 3. Anthropogenic changes in the pH, from the surface to 1,000 metres depth, over 15 years (1991-2006)”

    And the proof for this statement is where exactly???

    Just because something changes in the environment, it doesn’t mean the cause is anthropogenic.

    I am taking the findings of the paper at face value for purposes of discussion. If you’d like to know how they determine the anthropogenic component, please read the paper itself, where they describe it in some detail.

    w.

  61. One of the oddities of the paper that I noted is that their algorithm for determining the anthropogenic component shows that the deeper parts of the ocean are becoming more alkaline as a result of increasing CO2 … that I didn’t understand in the slightest. It was curious that they didn’t show what they claimed was the anthropogenic effect on water below 1000 feet …

  62. They are using spectrophotometric pH measurement and claim a precision of 0.001 pH units.

    I claim to be the smartest person on earth. But it may not be true.

    In any case, even if they can now measure to 0.001 units, the previous measurements were not taken with this accuracy. Any changes are just as dependent on the initial state. And a change of method may well introduce new errors on its own accord. To be accurate a change should be measured using the same equipment.

  63. [snip] – off topic
    So where now? Desperation, ocean acidification.
    ————–
    “Heck, even the name “acidification” is alarmist, because sea water is not acid, nor will it every be. What we are seeing is a slight reduction in how alkaline the sea water is.”
    —————
    Sea water is not acid? Good Lord, I’m glad someone told me.
    Indeed, a drop of arsenic in a bucket of water does not make it a bucket of arsenic.
    A warmer ocean holds less CO2. Ocean’s with less CO2 become more acidic, not acid.

    [Reply How can something become “more acidic” when it is not acidic to start with ? Dissolved carbon dioxide forms carbonic acid. How does less Co2 in the ocean make the ocean less alkaline? Just asking. RT – Mod]

  64. Regarding the Reply:

    “Ed MacAulay says:
    June 19, 2010 at 6:44 pm
    Now what if a subsea volcano or vent was slowly releasing gases and other materials?. Would it release sulfates, carbon dioxide or other pH modifiers? How would one separate that background level from the anthropogenic?”

    Ed,

    I can’t supply a link, but I recall reading about scientists studying the life thriving around a deep-sea vent. While studying some giant clams they noted a strange liquid oozing front a crack near the vent. Upon investigation, it turned out to be CO2, which is liquid under the extreme pressures of deep sea environments (as it is under the pressure inside a CO2 fire extinguisher.)

    Apparently the liquid CO2 did not form puddles on the sea bottom, but rapidly dissolved into the water. It had no apparent effect on the nearby deep-sea vent life forms. I have no idea what the Ph of the water was.

    Does anyone know more about this subject?

  65. Quotes from this blog post are in bold and my responses follow.

    Heck, even the name “acidification” is alarmist, because sea water is not acid, nor will it every be. What we are seeing is a slight reduction in how alkaline the sea water is.

    Acidification is the act of adding an acid to a solution, it has nothing to do with whether the solution is acidic or basic (i.e., basic, neutral, and acidic solutions can all be acidified by adding an acid to them). CO2 in water forms carbonic acid, so adding CO2 to the ocean is, well, ocean acidification. It’s not alarmist, it’s simply grammar.

    Likewise, cooling refers to a reduction in temperature. It doesn’t matter if the thing that is cooling was ‘hot’ or ‘cold’ to begin with, the reduction in temperature is, by definition, cooling. Addition of an acid to solution is, by definition, acidification.
    I’ve seen this quibble come up a few times lately, and why people bother to argue about it is a little beyond me. I mean, it’s as though we were having a discussion about the effects of overfishing and habitat destruction on stocks of sea horses around the world and a major complaint is that sea horses aren’t really horses. Really? Is that really worth complaining about?

    The first thing that I learned is that when you go from the tropics (Hawaii) to the North Pacific (Alaska), the water becomes less and less alkaline. Who knew? So even without any CO2, if you want to experience “acidification” of the ocean water, just go from Hawaii to Alaska …

    The reduction in pH from the Subtropical North Pacific to Northern Pacific driven almost entirely by increased CO2 concentration in the water. Changes in total alkalinity (more on this below)/salinity also have a small influence (i.e., Subtropical gyres have lower rainfall and thus higher salinity and total alkalinity than adjacent regions; total alkalinity increases with depth due to dissolution of carbonate minerals).
    This phenomenon is a result of oceanic circulation patterns, not simply as a result of latitude. The oldest (water mass age = time since it was in contact with the atmosphere) oceanic water upwells in the North Pacific. The older a water mass is the more organic material tends to be remineralized in it, and the higher the concentration of dissolved CO2. Hence dissolved CO2 is at about the highest concentration for any major oceanic water mass. By contrast, deep water forms in the North Atlantic. Similar transects through the Atlantic show little change in pH with latitude (nothing like the big decrease you see with increased latitude in the Pacific). pH decreases with depth because rates of photosynthesis (i.e., CO2 assimilation) decrease rapidly with depth (negligible below a few hundred meters) whereas rates of respiration (i.e., CO2 production) change more slowly. As a results, dissolved CO2 conc. increases with depth.

    To be clear: pH decreases due to increased CO2 concentration. The latitudinal pattern in the Pacific is driven by oceanic circulation while the depth pattern is driven by spatial patterns of photosynthesis and respiration.
    See, for example, Chemical Oceanography by Millero for a basic introduction to the patterns and driving forces.

    you didn’t notice the change from the “acidification”?

    The ecosystems change radically between the Subtropical and Northern Pacific as well as with depth at any given site. There are many, many environmental differences among these areas that drive these changes, the change in pH being one.

    You didn’t have your toenails dissolved by the increased acidity?

    Uh, straw man… Downing a tablet of uranium won’t dissolve anyone’s toenails either, therefore it is unimportant???

    Well, the sea creatures didn’t notice either. They flourish in both the more alkaline Hawaiian waters and the less alkaline Alaskan waters.

    Some species live near Hawaii while almost entirely different species live near Alaska, therefore the latitudinal/depth related pH structure is irrelevant? That’s like saying that since some archaea grow well near 90 C while ice fish live their lives at -1.8 C temperature is irrelevant to marine organisms. That’s just, well, silly.

    Changes in alkalinity/acidity are measured in units called “pH”. A neutral solution has a pH of 7.0. Above a pH of 7.0, the solution is alkaline. A solution with a pH less than 7.0 is acidic. pH is a logarithmic scale, so a solution with a pH of 9.0 is ten times as alkaline as a solution with a pH of 8.0.

    I wouldn’t be picky about terminology here, but since you incorrectly do so above, I suppose we’ll really strive for precision of language.

    Alkalinity (usually discussed, measured, and expressed as total alkalinity) is a property of sea water and is equivalent to the acid neutralizing capacity. See Chemical Oceanography by Millero for brief introduction to the meaning of “alkalinity” in oceanography. The term you want here, referring to how alkaline a sample is is “basicity”. The addition of CO2 to sea water has no effect on the alkalinity, but does lower the pH, therefore reducing the basicity (and increasing acidity). pH is way of expressing H+ activity (or concentration, depending on the scale—concentration on the seawater scale) and is unitless.

    pH is neutral where the activity of H+ equals the activity of OH-. Neutral pH is not inherently 7.0, but rather depends on significantly on temperature, pressure, and ionic strength. That is, neutral pH is 7.00 in completely pure water @ 25 C and 1 atm. Neutral pH in average seawater (S = 35 ppt, TA = 2300 ueq/kg) at a temp of 25 C and 1 atm is nearer 6.9. Exactly where the pH is neutral isn’t particularly meaningful though, it’s just a point of reference. For instance, a change in pH from 6.95 to 0.95 would have major effects chemistry/biology. A change from 7.01 to 6.99 (assuming 7.00 is neutral) would have much less of an effect, even though in the first case the solution was acidic the entire time whereas in the second the solution went form basic to acidic.

    The third thing I learned from the study is how little humans have changed the pH of the ocean. Figure 3 shows their graph of the anthropogenic pH changes along the transect. The full-sized graphic is here:

    The area of the greatest anthropogenic change over the fifteen years of the study, as one might imagine, is at the surface. The maximum anthropogenic change over the entire transect was -0.03 pH in fifteen years. The average anthropogenic change over the top 150 metre depth was -0.023. From there down to 800 metres the average anthropogenic change was -0.011 in fifteen years.

    This means that for the top 800 metres of the ocean, where the majority of the oceanic life exists, the human induced change in pH was -0.013 over 15 years. This was also about the amount of pH change in the waters around Hawaii.

    This is exactly what you’d expect though. The CO2 is coming in from the atmosphere, so the change at the surface is larger right now, since it takes time to mix surface water down through the ocean (turnover on the order of ~1000 yrs). The ~25 uatm increase in atmospheric CO2 over these 50 yrs (~353 to 378 uatm) should give you a -0.024 change in pH surface sea water (at equilibrium w/ atmosphere), all else equal. Sure enough, that’s what the data show. The change from the preindustrial atmospheric CO2 (280 uatm) to today (390 uatm) yields a pH change of -0.11.

    As you note above, since pH is measured on a logarithmic scale a small change in pH represents a comparatively large change in H+ activity/concentration. A -0.024 unit change represents a 5.7% increase in H+; a -0.11 change represents a 29% increase in H+. These changes certainly can and do impact chemistry, and likely at least some aspects of biology. Even so, if all we were talking about was a -0.024 change in pH, no one would care. That’s really not that big a deal, I think almost anyone would agree. A -0.11 change is a much bigger deal, and a >-0.4 change (>250% H+ increase), which is what we’ll get near the end of century on our current CO2 emissions trajectory, is much more substantial. A 6% increase in H+ probably isn’t anything to worry about if that’s all there will be, but a >250% increase in H+ (and the litany of other chemical changes it induces) is much more substantial. How biology reacts to this looks to be very complex, based on the work done so far, but there are a lot of data that suggest that this reduction in pH will cause many negative consequences for human society (a discussion in itself).

    Now, remember that the difference in pH between the surface water in Hawaii and Alaskan is 0.50 pH units. That means that at the current rate of change, the surface water in Hawaii will be as alkaline as the current Alaskan surface water in … well … um … lessee, divide by eleventeen, carry the quadratic resdual … I get a figure of 566 years.

    Why on Earth would you assume that the rate of change will be constant? The magnitude of the pH change resulting from the addition of CO2 to sea water depends on 1) the quantity of CO2 added and 2) the buffer intensity of the sea water (which depends, effectively, on starting pH). The rate that human activity is releasing CO2 to the atmosphere is increasing, and has been increasing more-or-less exponentially over the last century. To maintain the rate of pH decrease constant would require us to substantially reign in the rate of growth in CO2 emissions, something that doesn’t seem to be happening too fast, and something it seems like most of the folks here would be opposed to. We’re currently on track to see close to 0.50 unit pH reduction in surface waters by the end of the century (relative to the preindustrial, so a 0.4 reduction relative to today). That would reduce the surface pH to ~7.65 near Hawaii and ~7.25 near Alaska in 2100. That would be a pretty big change indeed. Also, a small point, but as mentioned above, the difference between mean surface pH of 8.05 (near Hawaii) and the minimum surface value of 7.65 (near Alaska) is 0.4, not 0.5 units.

    But of course, that is assuming that there would not be any mixing of the water during that half-millennium.

    No, all of the values above assume that there WILL be mixing. If there were no mixing then the reduction in surface ocean pH would be much larger than those I’ve mentioned above.

    The ocean is a huge place, containing a vast amount of carbon. The atmosphere contains about 750 gigatonnes of carbon in the form of CO2. The ocean contains about fifty times that amount.

    No, the ocean contains about fifty times as much dissolved inorganic carbon, but most of it is HCO3- (~92%) and CO3= (~7%). Little of the DIC in the ocean is CO2 (~1%). The ocean and atmosphere dynamically and substantially influence each other, no doubt about that. A perturbation in one yields a perturbation in the other.

    It is slowly mixed by wind, wave, and currents. As a result, the human carbon contribution will not stay in the upper layers as shown in the graphs above. It will be mixed into the deeper layers.

    But, that’s exactly what IS shown in these figures. The anthropogenic CO2 input is at the surface, but is slowly being mixed down into the ocean via normal circulation. Since the turnover time for the ocean is on the order of 1000 yrs and most of the CO2 input will occur in a century or two (or maybe three) the changes are larger and occur sooner at the surface, and slowly mix down.

    Some will go into the sediments. Some will precipitate out of solution.

    Adding CO2 to sea water shifts the equilibrium away from aragonite/calcite precipitation, reducing rates of sedimentation. Over the very long term (tens of thousands of years) most of the CO2 input will be removed via weathering of silicates. This is very important over the next 100,000 yrs, for example, but is pretty much irrelevant in our lifetime, our kids’, our grandkids’, etc.

    So even in 500 years, Hawaiian waters are very unlikely to have the alkalinity of Alaskan waters.

    As above, CO2 addition to sea water doesn’t directly affect alkalinity whatsoever. It reduces pH though. On our current trajectory, Hawaiian surface ocean pH will probably be near the current minimum surface ocean pH, that near Alaska. Alaskan waters would have a pH substantially lower than any current surface water pH. Again, the effects of these changes on biology requires another discussion, but suffice to say (for sake of not making this too terribly long) there are a lot of data that demonstrate that is likely to be a very big deal indeed.

    The final thing I learned from this study is that creatures in the ocean live happily in a wide range of alkalinities, from a high of over 8.0 down to almost neutral.

    You mean pH, not alkalinity. Like above, observing that there is *something* alive over a wide pH range and suggesting that pH is not an important factor in structuring the ocean is just silly. There are archaea doing well at 90 C and ice fish thriving at -1.8 C. Change those temperatures much and they’re both toast.

    As a result, the idea that a slight change in alkalinity will somehow knock the ocean dead doesn’t make any sense.

    Again, you mean pH, not alkalinity. This is a straw man though—no one is saying that a small change in pH will ‘knock the ocean dead.’ A big decrease in pH, like what we are going to see this century without a substantial change in behavior, has been shown to have a variety of negative effects on a variety of organisms.

    By geological standards, the CO2 concentration in the atmosphere is currently quite low. It has been several times higher in the past, with the inevitable changes in the oceanic pH … and despite that, the life in the ocean continued to flourish.

    First, atmospheric CO2 is only one of the components that determines sea water pH. Total alkalinity is also critically important, and it has almost certainly been a fair amount higher in the pas as well. Ocean pH has certainly been lower in the geologic past, but pH is but one of many factors that was significantly different and that affected, for instance, biomineralization. At the times when CO2 was substantially higher in the geologic past, so was calcium concentration and likely total alkalinity as well. It’s easy to produce carbonate minerals in those conditions, must as it is easy today. However, when you combine low pH with (geologically) low calcium and alkalinity, which would be the situation as silicate weather catches up over tens of thousands of years, it’s not so easy to produce and preserve carbonate minerals.

    We also cannot measure physiological processes in organisms that lived 50, 100, 500 million years ago. They lived in an ocean with a lower pH than ours, and it’s likely that their physiology adapted over evolutionary time to those conditions. We can’t much for certain because, well, they’re all extinct, and have been for millions of years. What we can do is measure the responses of modern organisms to the conditions they are likely to be seeing in a few decades. When we do that we see that, in fact, many organisms do very poorly indeed in this low pH brave new ocean.

    Best,

    Chris

  66. CO2 says:
    June 20, 2010 at 1:50 am

    Sea water is not acid? Good Lord, I’m glad someone told me.
    Indeed, a drop of arsenic in a bucket of water does not make it a bucket of arsenic.
    A warmer ocean holds less CO2. Ocean’s with less CO2 become more acidic, not acid.

    Reply How can something become “more acidic” when it is not acidic to start with?
    Dissolved carbon dioxide forms carbonic acid. How does less Co2 in the ocean make the ocean less alkaline?
    Just asking. RT – Mod

    And now I’m out of moderator mode I’d just like to add that you’d think someone posting under the name CO2 would get this rght!

    Sheesh!

  67. I noticed the charts are attributed to a group I’ve been trying to keep an eye on for the last 3 months. CLIVAR.

    CLIVAR is Climate Variability and Predictability. A World Climate Research Programme of INTERNATIONAL COUNCIL FOR SCIENCE.
    INTERGOVERNMENTAL OCEANOGRAPHIC COMMISSION,
    and WORLD METEOROLOGICAL ORGANIZATION.

    Their website is HERE

    From their handbook…

    CLIVAR is an international research programme investigating climate variability and predictability on time-scales from months to decades and the response of the climate system to anthropogenic forcing. CLIVAR, as one of the major components of the World Climate Research Programme (WCRP), started in 1995 has a lifetime of 15 years.
    The specific objectives of CLIVAR are:
    1. To describe and understand the physical processes responsible for climate variability and predictability on seasonal, interannual, decadal, and centennial time-scales, through the collection and analysis of observations and the development and application of models of the coupled climate system, in cooperation with other relevant climate-research and observing programmes.
    2. To extend the record of climate variability over the time-scales of interest through the assembly of quality-controlled paleoclimatic and instrumental data sets.
    3. To extend the range and accuracy of seasonal to interannual climate prediction through the development of global coupled predictive models.
    4. To understand and predict the response of the climate system to increases of radiatively active gases and aerosols and to compare these predictions to the observed climate record in order to detect the anthropogenic modification of the natural climate signal.

    They are well funded, with a number of ships and aircraft at their disposal. I came across CLIVAR whilst taking part in the Citizens Audit Project.
    The CLIVAR objectives immediately reminded me of the Kevin Trenberth article “More Knowledge Less Certainty” in Nature Reports Climate Change Published online: 21 January 2010 | doi:10.1038/climate.2010.06 HERE where he states

    “But for its fifth assessment report, known as AR5 and due out in 2013, the UN panel plans to examine explicit predictions of climate change over the coming decades. In AR5′s Working Group I report, which focuses on the physical science of climate change, one chapter will be devoted to assessing the skill of climate predictions for timescales out to about 30 years

    My immediate thoughts were, “wow, imagine if this lot fluked just one El Nino, or a drought somewhere, you can see the headlines now,

    ‘researchers prediction comes true, man responsible’ etc etc

    Some of the usual suspects are with the CLIVAR programme, Meehl, Karoly, Briffa, Mann, P Jones, Neville Nichols. NOAA, CSIRO, NCAR, UEA, HADLEY, UK MET BoM etc etc

  68. Chris says:
    June 20, 2010 at 2:15 am

    Again, the effects of these changes on biology requires another discussion, but suffice to say (for sake of not making this too terribly long) there are a lot of data that demonstrate that is likely to be a very big deal indeed.

    Chris, do feel free to post links to studies on this or any of the other points you addressed. It’s more useful than general arm waving. Just type in the web address, no need for code tags.

    Thanks

  69. They are starting up a new institution now in Norway to study “ocean acidification”.

    Its gonna cost us millions upon millions. The socialist mr. Solheim is behind it.
    So there is a political pressure. Its gonna replace the Globull Warning scare,
    because they can see that this scare is running out of steam.

    So prepare for a lot of Globull Acidification Scare (GAS) in the future.
    It will originate from these new institutions.

    They have a budget, you see. And they will have lead authors in the new UN panel.
    And they will approve their own reports.

    It will be thousands of pages.And thousands of scientists will be behind it.
    Just wait and see.

    It will be in school-books shortly.

  70. Amazing how different compounds interact with water and pressure and temperature.
    When doing any studying on water itself, it is very complex as it can hold trace elements as well as have the capacity to saturate with soluable compounds, yet repel other compounds.

  71. We also cannot measure physiological processes in organisms that lived 50, 100, 500 million years ago. They lived in an ocean with a lower pH than ours, and it’s likely that their physiology adapted over evolutionary time to those conditions. We can’t much for certain because, well, they’re all extinct, and have been for millions of years. What we can do is measure the responses of modern organisms to the conditions they are likely to be seeing in a few decades. When we do that we see that, in fact, many organisms do very poorly indeed in this low pH brave new ocean.

    Oh dear eg Hendricks and Rickaby

    Abstract. An urgent question for future climate, in light of
    increased burning of fossil fuels, is the temperature sensitivity
    of the climate system to atmospheric carbon dioxide
    (pCO2). To date, no direct proxy for past levels of pCO2 exists
    beyond the reach of the polar ice core records. We propose
    a new methodology for placing a constraint on pCO2
    over the Cenozoic based on the physiological plasticity of
    extant coccolithophores. Specifically, our premise is that the
    contrasting calcification tolerance1 of various extant species
    of coccolithophore to raised pCO2 reflects an “evolutionary
    memory” of past atmospheric composition. The different
    times of evolution of certain morphospecies allows an upper
    constraint of past pCO2 to be placed on Cenozoic timeslices.
    Further, our hypothesis has implications for the response of
    marine calcifiers to ocean acidification. Geologically “ancient”
    species, which have survived large changes in ocean
    chemistry, are likely more resilient to predicted acidification.

    ….Coupling of calcification
    with species-specific Rubisco specificity provides
    a tangible means to preserve the CO2/O2 composition at the
    time of origin of photosynthetic phyla (Giordano et al., 2005;
    Tcherkez et al., 2006). The preservation of calcification ability
    at high pCO2 in C. pelagicus may occur through genetic
    redundancy (Wagner, 1999), or variance in genetic expression
    whilst the adaptation of E. huxleyi and C. leptoporus to
    the modern low pCO2 niche could be associated with gene
    inactivation of pathways associated with high pCO2 (Hittinger
    et al., 2004). The high proportion of duplicate genes
    within plant and algae genomes is indicative of a high rate
    of retention of duplicate genes (Lynch and Connery, 2000).
    Gene duplications contribute to the establishment of new
    gene functions, and may underlie the origin of evolutionary
    novelty. Duplicate genes can exist stably in a partially redundant
    state over a protracted evolutionary period (Moore
    and Purugganan, 2005). A half-life to silencing and loss of
    a plant gene duplicate is estimated at 23.4 million years such
    that remnant duplicate genes, which can be reactivated by
    environmental conditions to encode calcification within coccolithophores
    under “ancestral” conditions representative of
    60 Ma, appears reasonable…..

    ….an advantage over the now prosperous E. huxleyi, as the carbonate
    system of the ocean reverses towards the acidity of the
    past. C. pelagicus has weathered large and abrupt changes in
    conditions in the geological past, e.g. the Palaeocene-Eocene
    thermal maximum (Gibbs et al., 2006), with no apparent impact
    on physiology, but the adaptive strategies of newcomer
    E. huxleyi may differ significantly, potentially leading to future
    non-calcifying descendants.

  72. Chris says:
    June 20, 2010 at 2:15 am

    Great post, I made a start on something similar, but you’ve done it far, far better and saved me a lot of research, many thanks. This is a red herring, a desperate diversion from the evolving situation in the arctic. I’m awaiting the results from the last Catlin survey.

  73. kwik says:
    June 20, 2010 at 3:16 am

    ” Its gonna replace the Globull Warning scare,
    because they can see that this scare is running out of steam.
    So prepare for a lot of Globull Acidification Scare (GAS) in the future.
    It will originate from these new institutions.”
    —————-
    The sceptical arguments are the ones running out of steam; this global warming conspiracy is ranging wider and wider, including biology and chemistry. How do you imagine that thousands of scientists can form a conspiracy? Usually a conspiracy works best with the fewest number of conspirators; like 2.

  74. CO2 says:
    June 20, 2010 at 1:50 am

    Sea water is not acid? Good Lord, I’m glad someone told me.
    Indeed, a drop of arsenic in a bucket of water does not make it a bucket of arsenic.
    A warmer ocean holds less CO2. Ocean’s with less CO2 become more acidic, not acid.

    Reply How can something become “more acidic” when it is not acidic to start with?
    Dissolved carbon dioxide forms carbonic acid. How does less Co2 in the ocean make the ocean less alkaline?
    Just asking. RT – Mod
    —————————
    Please read; Chris says: June 20, 2010 at 2:15 am, quite informative.
    Don’t confuse acidic with alkaline.
    ————————
    And now I’m out of moderator mode I’d just like to add that you’d think someone posting under the name CO2 would get this rght!

    Sheesh!
    ——————-
    Have you read the post? Now I pose the reverse question, Sheesh!
    ——————–

  75. “CO2 says:
    [...]
    How do you imagine that thousands of scientists can form a conspiracy? Usually a conspiracy works best with the fewest number of conspirators; like 2.”

    You’re right there; ClimateGate has proven that their attempts to conspire get blown sooner or later. Of course it was also proof that they did conspire.

  76. John Silver says:
    June 20, 2010 at 3:50 am
    I wonder when the Mob is going to move in and take over this science racket?

    From reports I’ve seen the Mafia already has near dominance of “Green Energy” in the EU. Like Willie Sutton, they know where the money is.

  77. John Silver says:
    June 20, 2010 at 3:50 am
    I wonder when the Mob is going to move in and take over this science racket?

    They did dude! Called themselves the IPCC.

  78. CO2 says:
    June 20, 2010 at 4:21 am

    CO2 says:
    June 20, 2010 at 1:50 am

    Sea water is not acid? Good Lord, I’m glad someone told me.
    Indeed, a drop of arsenic in a bucket of water does not make it a bucket of arsenic.
    A warmer ocean holds less CO2. Ocean’s with less CO2 become more acidic, not acid.

    Reply How can something become “more acidic” when it is not acidic to start with?
    Dissolved carbon dioxide forms carbonic acid. How does less Co2 in the ocean make the ocean less alkaline?
    Just asking. RT – Mod

    Please read; Chris says: June 20, 2010 at 2:15 am, quite informative.
    Don’t confuse acidic with alkaline.

    And now I’m out of moderator mode I’d just like to add that you’d think someone posting under the name CO2 would get this rght!

    Sheesh!

    Have you read the post? Now I pose the reverse question, Sheesh!

    Heh, some people don’t know when to stop digging and simply admit they got it wrong.

    Yes Mr “CO2″, Chris’ use of acidification is grammatically correct, However your assertion that “Ocean’s with less CO2 become more acidic” is not. It’s wrong on two counts.

    1) if the ocean is not acidic to begin with (it isn’t) , then it can’t become “more acidic”, only less alkaline. It can undergo a process of acidification however, as Chris said.

    2) (And you didn’t try to address this one, presumably because you know you’ve been caught with your pants round your ankles) Co2 dissolved in water forms an acid. Yet you state that “A warmer ocean holds less CO2. Ocean’s with less CO2 become more acidic”.

    So to repeat my question: How does removing an acid forming compound from the ocean make the ocean “more acidic”(sic).

    Now I pose the reverse question

    Well you’ve got everything else back to front, so why not?

  79. CO2 says:
    June 20, 2010 at 4:02 am
    The sceptical arguments are the ones running out of steam; this global warming conspiracy is ranging wider and wider, including biology and chemistry. How do you imagine that thousands of scientists can form a conspiracy? Usually a conspiracy works best with the fewest number of conspirators; like 2.

    You have no idea of how much surpressed science and non-peer reviewed science that is already out there. The peer review process that the current science is using to keep government grants into each others hands, supresses good science as who is an expert in unknown field of study? Science has yet to even look at the mechanical aspects of this planet and solar system. Our basic scientific LAWS just do not stand up against time and basic measurements of distance.
    Just say the word “ROTATION” and a fog goes over knowledgable people.

  80. Willis, another thought on this paper. Rainwater has a pH that ranges from 4.5 – 5.5. It seems to me that the entire variation measured in the paper (particularly the changes in pH near the surface) could be caused by small changes in precipitation rates along the chosen transect, between the two sampling times. In other words, natural variability in local ocean pH, driven partly by precipitation dynamics over monthly, annual and decadal timescales, is being woefully under-sampled in this study.

  81. DirkH says:
    June 20, 2010 at 4:33 am

    “CO2 says:
    —————–
    Conspiracy is an assumption made by the desperate having no proof, it’s rarely proven. By its nature a conspiracy is secret. Give me an idea as to how you you imagine the thousands of scientists to conspire. Do they have a rather large meeting place? Three independent investigations have cleared the East Anglia CRU. Advise me what proof you have of a conspiracy other than repeating a conspiracy throw away.

  82. kwik says:
    June 20, 2010 at 3:35 am

    How I wish that Roy Spencer is right, for the sake of the world, but how I recognise my own wishful thinking. This man is a discredited voice and yes, I have studied all his claims.

  83. “CO2 says:
    [...]
    “Three independent investigations have cleared the East Anglia CRU. Advise me what proof you have of a conspiracy other than repeating a conspiracy throw away.”

    Read the ClimateGate e-mails. They conspired to put a journal out of business, for instance, and they conspired to skew the peer review process. I mean, why do i talk to you. You sound like the Black Knight; you simply ignore things that happen. That won’t help the warmist movement one bit. A movement led by a crazy nutter like Hansen, how would one ever expect such people to be in touch with reality in the first place.

    BTW who are “the thousands of scientists ” and why do you carry that silly number around with you as if it means something? Are you that easily impressed? Where do you have that number from?

  84. Willis,

    What makes you say the pH change is human-induced? Jump to conclusions much?

    You’ll note that the deep water, which by the way comprises 90% of all ocean water, has very little change over latitude and is substantially less alkaline than the surface waters. Isn’t it quite possible, or even likely, that the less alkaline depths are simply mixing more or less with the surface layer? Surely you know that there’s a vast oceanic conveyor belt that mixes the two layers. Do we know, other than coriolis force plus equatorial heating and polar cooling which are the main drivers, what factors serve to change the amount of mixing? Wind is one thing. If the warmists are correct that more surface heat creates more severe weather then we should expect a negative feedback as the winds cause more mixing of warm surface water with the almost freezing cold depths.

    We know there are cyclical events like ENSO, PDO, and AMO with somewhat variable cycle times from years to decades. What drives the variability? To believe that a tiny fraction more CO2 in the atmosphere, which may or may not be due to human activity, is responsible is both unwarranted and unlikely. To believe such a thing with religious fervor and conviction is indicative of someone not playing with a full deck if you ask me.

  85. Leonid Polyak of OSU’s Byrd Center (“History of Sea Ice” survey in QSR 2010) recently kindly referred me to two articles on pre-pleistocene CO2 atmospheric concentrations by Dana Royer et al, in GSA Today March 2004 (v. 14 no 3, p4ff), and (solo) in Geochimica et Cosmochimica Acta 2006 (v. 70: 5565-75, as providing a good summary of knowledge of pre-Vostok CO2 levels.

    According to the estimates Royer cites, CO2 concentrations were in excess of 500 ppm and often in excess of 1000 ppm for most of the last 500M years. During much of the Paleozoic, the point estimates (with a huge error band) run about 4000 ppm, while the Mesozoic ran mostly 1000-2000 ppm (with a big error band). The only times it has been comparable to pre-1950 levels have been glacial periods — the Neogene and the late-Carboniferous-Permian glacials. Royer proposes 1000 ppm as being the threshold for “the initiation of globally cool events” and 500 ppm as the threshold for “full glacials”.

    Of course it’s hard to separate cause and effect — do fluctuations in CO2 (due to vulcanism, weathering, and fossil fuel and limestone formation) cause fluctuations in temperature through the GHG effect, or do fluctuations in temperature (from orbital, solar, and other causes) cause CO2 to be outgassed from the oceans?

    But be that as it may, most of the world’s limestone was somehow laid down when atmospheric CO2 was at least twice the current elevated levels. How could this have occurred in such an “acidic” ocean environment if CO2 alarmists are right?

    Furthermore, if 500 ppm is the threshold required to prevent the Pleistocene Curse of recurrent Ages, shouldn’t we be shooting for that level as a positive goal? “Cool” sounds good, so I’d be concerned if we were heading over 1000 ppm.

    On a purely semantic note, Willis, my recollection from chem lab is that if you add an acid to an alkaline solution, you are “acidfying” it, even if it remains basic. So it doesn’t bother me to say that adding CO2 to the atmosphere and thence to sea water will “acidify” it.

    But I do wonder, however, how low ocean pH could get even if the atmosphere were pure CO2 — carbonic acid is very weak in comparison to nitric or sulphuric, so I don’t think it would get you very far. Willie Soon claims that many alarming studies of the adverse effect of acidification on mollusk shells resort to these strong acids to achieve an unrealistically low pH. What’s the pH of club soda, anyway?

  86. @ CO2

    Conspiracy is an assumption made by the desperate having no proof, it’s rarely proven.

    If by that you the conspiracy theory that big oil is paying all the skeptics then I’ll agree it’s a sure sign made by the desperate who have no proof. Climategate is small potatoes and less than a year old in comparison to the big oil conspiracy theory. Hide your decline much?

  87. CO2 says:
    June 20, 2010 at 5:32 am

    Conspiracy is an assumption made by the desperate having no proof, it’s rarely proven.

    If by that you mean the conspiracy theory that big oil is paying all the skeptics then I’ll agree it’s a sure sign made by the desperate who have no proof. Climategate is small potatoes and less than a year old in comparison to the big oil conspiracy theory. Hide your decline much?

  88. Commenting on Dr Spencer, CO2 says:

    “This man is a discredited voice and yes, I have studied all his claims.”

    Your ad-hom opinion means nothing without verifiable facts. Since you are a self-described expert on Dr Spencer, please share with us the identities of all those people who have ‘discredited’ him, and state exactly why. Provide scientific facts, please, without your character-assassinating innuendo.

  89. “The sea is a complex, buffered environment in which the pH” (and everything else) “is changing constantly.”

    And yet, today, Sunday, June 20, 2010, science is truly settled. We are wallowing in a near lifeless state on the bottom of a deep cesspool, our heart rate is so faint as to be nearly undetectable. We have arrived. We are as the gods, the master of all we survey. Nothing new will ever be known again.

  90. This interesting note on the role of bicarbonate [from wisegeek.com]

    “Carbonic acid plays an important role in keeping the body’s pH stable. The normal pH of bodily fluids is around 7.4 and must be kept close to this value in order for the body to function properly. If the pH changes, whether up or down, enzymes can stop functioning, muscles and nerves can start weakening, and metabolic activities becomes impaired. The bicarbonate ion released from carbonic acid serves as a buffer that helps resist changes in pH. This means it can act as an acid or a base as the need arises.

    Acids are defined as any substance that releases hydrogen ions into solutions. Bases are accepts those hydrogen ions. When excess hydrogen ions build up in the body—i.e. the fluids become more acidic—then bicarbonate ions accepts those extra hydrogen ions and keeps the body’s pH at a normal level. In the inverse, if the hydrogen ion levels drop too much—i.e. the fluids become too alkaline—then carbonic acid gives up hydrogen ions in order to keep the blood’s pH normal. This process is also seen during the transport of oxygen and carbon dioxide.

  91. CO2 says:
    June 20, 2010 at 5:42 am

    How I wish that Roy Spencer is right, for the sake of the world, but how I recognise my own wishful thinking. This man is a discredited voice and yes, I have studied all his claims.

    Have you ‘studied’ them as carefully as the effect of removing co2 on ocean ph, CO2?

  92. Is this the right time for the unearthing of the Acid Rain tome?
    It would seem that there are a lot of folks who have no understanding whatsoever of basic chemistry. Everybody grab their pH papers! Head for the nearest shoreline.

  93. >> CO2 says:

    Conspiracy is an assumption made by the desperate having no proof, it’s rarely proven. By its nature a conspiracy is secret. Give me an idea as to how you you imagine the thousands of scientists to conspire. Do they have a rather large meeting place? Three independent investigations have cleared the East Anglia CRU. Advise me what proof you have of a conspiracy other than repeating a conspiracy throw away. <<

    First, YOU were the one who brought up 'conspiracy', so it's a straw man argument to begin with.

    Secondly, it doesn't take thousands of scientists conspiring to control the direction of research, it takes only those few who control the bulk of the funding. If the funding is only going to those who agree with a hypothesis, and scientists need to bring in grant money to get tenure and continue their careers, guess which hypothesis those scientists who keep their jobs (and are thus able to publish) are going to agree with?

    If you need an example, consider the Catholic Church. There are essentially no priests who disagee with the tenets of the Church. It does not require a conspiracy among the thousands of priests to maintain that, it only requires the disbelievers get weeded out early in the process. In the religion of Global Warming, the skeptics also get weeded out early.

  94. sdcougar says:
    June 20, 2010 at 7:22 am
    This interesting note on the role of bicarbonate [from wisegeek.com]

    “Carbonic acid plays an important role in keeping the body’s pH stable. The normal pH of bodily fluids is around 7.4 and must be kept close to this value in order for the body to function properly. If the pH changes, whether up or down, enzymes can stop functioning, muscles and nerves can start weakening, and metabolic activities becomes impaired. The bicarbonate ion released from carbonic acid serves as a buffer that helps resist changes in pH. This means it can act as an acid or a base as the need arises.

    A common misconception, the carbonic acid system doesn’t act as a chemical buffer to keep blood pH around 7.4. Buffers operate to maintain the pH near their pKa, the pKa of the carbonic acid system is ~6.4, a factor of 10 out!

  95. Now that Nina seems to be arriving and if she hangs around , I see the CO2 levels plateauing or dropping..
    Remember Cold, bad, warm, good….
    Check out the new Nat’l Geo for their latest AGW ! Greenland is melting! scary
    story….

  96. Hu McCulloch says:
    June 20, 2010 at 6:58 am

    “What’s the pH of club soda, anyway?”

    The pH of water under a pure CO2 atmosphere at one atmosphere is about 4.

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

    The issue of ocean pH relates to the level of understanding of the buffering mechanisms in sea water.

    I’ve had several discussions on various blogs with regard to buffering and “precision” of pH measurements. The question sometimes leads to a knee-jerk response of derision just for asking the question.

    http://landshape.org/enm/errors-adding-up/

    But there are reasonable references out there that describe what’s needed to measure pH at the levels necessary.

    http://climateaudit.org/2008/09/23/sea-ice-end-of-game-analysis/?cpage=15#comment-163882

    To make a long story short, there’s a reason you’re unlikely to see any graphs of long term pH trends with uncertaintly bars included.

  97. The best reference I’ve found for measuring pH is here.

    http://aslo.org/lomethods/free/2004/0126.pdf

    One would have to follow my links above a bit deep to find it.

    In this reference, the first full paragraph on p. 135 is an honest exposition of some remaining problems with the technique, including the possibility that there could be species in sea water that aren’t fully accounted for in the models.

    “A more speculative explanation for the discrepancy could be acid-base
    systems not reflected in the alkalinity calculation but perhaps present in surface waters.”

  98. Hu McCulloch says:
    June 20, 2010 at 6:58 am
    But I do wonder, however, how low ocean pH could get even if the atmosphere were pure CO2 — carbonic acid is very weak in comparison to nitric or sulphuric, so I don’t think it would get you very far. Willie Soon claims that many alarming studies of the adverse effect of acidification on mollusk shells resort to these strong acids to achieve an unrealistically low pH. What’s the pH of club soda, anyway?

    The pH of most carbonated drinks is around 3, Cola drinks also contain phosphoric acid. One of my students had a problem with a steel bowl that had got a little rusty due to neglect and asked my advice about cleaning it, I suggested using Coke. Much to his surprise it did a beautiful job!

  99. Phil. says:
    June 19, 2010 at 10:33 pm

    flyfisher says:
    June 19, 2010 at 8:53 pm
    One other thing to consider: what is the standard error of their equipment? I’d be astounded if their measurement device was accurate below 0.01 pH Units.

    Perhaps you should have read the paper (specifically Data and Methods):

    “Measurement precision on both transects was on the order of ±0.001″

    Phil,

    give up now, you obviously have no knowledge of what you are demanding that everyone else accepts without question.

    pH CANNOT be measured to 0.001 units. The buffer solutions used to calibrate electrodes are only accurate to +/- 0.1 pH units, and that is recognized in international standards.

    If you look at the sentence you pulled from that paper, it would seem to refer to location, i.e. longitude and latitude

  100. Verity Jones says:
    June 20, 2010 at 12:21 am
    “A thought – aquariums (the large public kind, not living-room sized) often have displays of tropical fish and corals. These are often in areas of colder (less alkaline) water (e.g. Seattle Aquarium). Presumably these use local seawater, filtered and heated, which may change the pH. While such large tanks are hardly natural ecosystems, corals don’t seem to ‘struggle’ in such environments. OK, perhaps they carefully control the pH and pCO2. Can anyone provide an insight?”

    Some do (control the pH).

    However, healthy, growing corals are regularly kept by hobbyists in marine aquaria. Aquaria are usually kept indoors, where CO2 levels are often many times higher than in the atmosphere.

    To successfully keep stony corals in an aquarium you must somehow add Ca and HCO2 ions to make up for those deposited by the corals. One of the most common ways to do that is to dissolve lime stone using CO2 in a special reactor. Such aquariums tend to have considerably lower pH than natural sea water, but very healthy corals.

    One of the older methods (Jaubert method) of adding Ca and HCO3 in hobby aquariums involve enhancing the natural pH variations, with low pH during the night. Presumably lime stone is dissolved in isolated pockets of water and diffuse into the aquarium.

    In both cases, stony corals thrive under much lower pH conditions than we will ever see as a result of “ocean acidification”.

    (A third common method of stony coral keeping involves dripping dissolved Ca(OH)2 into the aquarium. Aquaria kept using this method will have higher pH conditions than natural sea water – and thriving corals.)

  101. tallbloke says:
    June 20, 2010 at 5:01 am

    CO2 says:
    June 20, 2010 at 4:21 am

    CO2 says:
    June 20, 2010 at 1:50 am
    “2) (And you didn’t try to address this one, presumably because you know you’ve been caught with your pants round your ankles) Co2 dissolved in water forms an acid. Yet you state that “A warmer ocean holds less CO2. Ocean’s with less CO2 become more acidic”.
    ——————
    I should have added, “Because of other factors”, a warmer ocean…
    Ocean acidity is not only a simple function of CO2 disolving in water, it involves the bio-mass from Phyto-plankton and Zooplankton down, which sequester CO2 drawing on the disolved CO2 carrying it to both the deep waters and the ocean floor. This is referred to as the solubility pump and the biological pump. This bio-mass of Phytoplankton and Zooplankton, residing close to the surface, is threatened by the warming of colder oceans, resulting in less absorbtion of CO2, increasing the disolved CO2 level, hence acidity. The whole issue is far more complex than a discussion about Ph, acidity and alkaline. While a warmer ocean may absorb less CO2, the CO2 level will still increase if the rate of sequestration drops disproportionally.
    ——————
    1) if the ocean is not acidic to begin with (it isn’t) , then it can’t become “more acidic”, only less alkaline. It can undergo a process of acidification however, as Chris said.
    —————–
    This is just playing with words; what’s the difference between ‘a process of acidification’ and more acid? As for the pants, they don’t need ironing yet.

  102. Tom_R says:
    June 20, 2010 at 7:44 am

    >> CO2 says:
    ———————-
    I brought up conspiracy? I thought Lord Christopher Monckton invented that.

  103. DirkH says:
    June 20, 2010 at 6:13 am

    “CO2 says:

    BTW who are “the thousands of scientists ” and why do you carry that silly number around with you as if it means something? Are you that easily impressed? Where do you have that number from?

    ——————–
    You mean like the 32000 anti global warming scientists petition, which included an Archbishop of Australia? As for scientists supporting human induced global warming, just Google it.

  104. Ed Caryl says:

    “If I’ve got this straight, points in the ocean that are acidifying must be cooling?”

    The colder portions are more acidic. The bigger changes, according to the data above, are in the warmer regions of the ocean. However, there’s something I want to address about concentration change later in this post.

    Phil says:

    “However you’ve forgotten that the equilibrium concentration of CO2 in the surface water is also dependent on the pCO2 in the atmosphere which is being steadily increased by fossil fuel combustion.”

    I didn’t forget it, but I didn’t state it as well as I should have. The absorption of CO2 into the ocean is less in warmer waters, but you’re correct in stating greater CO2 concentration will dissolve more CO2 in the water. So when I say it’s self-regulating, it’s due to the competing forces of the equilibrium of increased CO2 and the decreased dissolved CO2 in warmer water.

    —–

    Now that all being said, there’s been some griping and percentage of pH change. Yes, pH is a logarithmic scale. But look at the absolute concentration of H3O+ in the warmer latitutes. The pH is 8.0 at its maximum, which is 0.00000001 M, compared to that of the northern latitude, which is 0.0000000398 M. (M is molarity, or Moles of H3O+ per liter.) Changes here are amazingly small.

    To give you an idea, one mL of 1.0 M HCl has a pH of 0. If I dilute that to 1 L with water, the pH becomes 3.0. If I dilute it to 1000 L, my pH is now 6. as you can see, the concentration of H3O+ is minute at those levels, and it’s even smaller at the pH range between 8 and 7.4. Calling a shift of 0.02 pH significant is laughable because the actual moles per liter change of H3O+ is so small that it falls within margins of error of the devices used to measure pH.

  105. A correction :You didn’t have your toenails dissolved by the increased acidity?

    Proteins (human body) dissolves in the alkaline pH range. The process to extract protein from various sources it is based on this fact: Protein dissolves above pH=8, and it is decomposed in its “salts” of the alkali used, forming amminoates from the aminoacids which were assembled forming the protein. What it is not commonly known is that proteins become re-assembled again, when pH lowers to 4,5-4,6.

    http://www.ams.usda.gov/AMSv1.0/getfile?dDocName=STELPRDC5057645

  106. Another precision: pH accounts for the free H+ (protons) dissolved (ionized) in a solution and OH- accounts for the free OH- (electrons) dissolved (ionized) in a solution. Think of water in clouds, arranged (polarized) in such a way to allow thoundsands of tons of water to defy gravity.
    Think this post shows a relation of temperature (degree of activity) to pH.

  107. Such an interesting array of comments.

    @CO2 – You don’t need a “conspiracy”, all you need is grant funding for only one point of view.

    I would venture that the temp of the water varies as you travel from Hawaii to Alaska as does the composition of plants and animals in the top 150 meters of water. Why…I bet even the depth of the water and whatever is on the bottom varies as well. Then we have varying current and oscillations, the thermohaline, etc. In fact, I wouldn’t be surprised if the salinity of the ocean didn’t vary along this transect.

    Folks need to go back to college chemistry and re-learn how buffer systems work. I’ve just read some pretty lame “explanations” in support of ocean acidification (including my favorite, the pCO2 change due to anthropogenic CO2). This is a matter of scale and you can test it in a laboratory. Cook up some sea water, buffer it and place it in a chamber. You can crank the CO2 conc in the chamber all the way up to 700 ppm (without changing the ambient air pressure) and let it cook for a month and you won’t be able to measure a change in pH.

  108. Chris says:
    June 20, 2010 at 2:15 am

    Quotes from this blog post are in bold and my responses follow.

    Heck, even the name “acidification” is alarmist, because sea water is not acid, nor will it every be. What we are seeing is a slight reduction in how alkaline the sea water is.

    Acidification is the act of adding an acid to a solution, it has nothing to do with whether the solution is acidic or basic (i.e., basic, neutral, and acidic solutions can all be acidified by adding an acid to them). CO2 in water forms carbonic acid, so adding CO2 to the ocean is, well, ocean acidification. It’s not alarmist, it’s simply grammar.

    Chris, you are grasping at straws. As I said above, the point is that it is alarmist terminology. It leads people who think the ocean is neutral to be fearful that the ocean is turning into an acid.

    This, and your long, long list of nitpicks above (yes, 7.0 is only neutral in pure water at 25°C, and in the ocean it’s about 6.9 … so what?) are generally technically correct and totally meaningless. The point is simple. The change in oceanic basicity is so small and so slow that it will not affect much of anything. In many places, including coral reefs, the ocean sees larger pH changes daily than the total change projected from changing CO2 over the next century.

    There is one misconception of yours I do want to clear up, however. You say:

    But of course, that is assuming that there would not be any mixing of the water during that half-millennium.

    No, all of the values above assume that there WILL be mixing. If there were no mixing then the reduction in surface ocean pH would be much larger than those I’ve mentioned above.

    You speak in hushed tones about how

    A -0.11 change is a much bigger deal, and a >-0.4 change (>250% H+ increase), which is what we’ll get near the end of century on our current CO2 emissions trajectory, is much more substantial.

    According to the references I’ve seen, if the atmospheric CO2 were to double instantaneously, the oceanic surface pH would go down by about 0.26, not 0.4. This is much less than a month’s pH change in the Monterey Bay seawater. But the extra CO2 in the surface would eventually mix throughout the ocean, reducing the atmospheric CO2 and increasing the surface basicity (your preferred term).

  109. Why is the pH lower at depth?

    Probably more a factor of water temperature as warmer water contains more dissolved salt so cooler water at greater depths and in northern latitudes tends to be less alkaline.

  110. Thanks Willis for some interesting data and insight

    One could almost guess that CO2 is more soluble in colder water; maybe you should do some research on that.

    Several people have mentioned the surface CO2 “mixing” with the deeper water. I’m sue it happens; but no need to even invoke “mixing”.

    As weak as my chemistry is, I still understand from solid state Physics how diffusion driven by a concentration graient, works. When you have people dancing in a bunch on the ballroom floor, and there’s an open space; the dancers naturally gravitate towards the empty space. Well in the ballroom case, that simply moves the empty space to somewhere else; but in an ocean situation, if you have CO2 dissolving in warmer surface water per Henry’s law; and you have a temperature relapse rate with depth (for while); it is perfectly natural for that higher concentration CO2 at the surface to move under diffusion to the colder deeper water where it is even more soluble.

    So the ocean temperature relapse rate is a natural pumping mechanism that actually drives CO2 from the surface to the deep er waters. You don’t even have to invoke convection (mixing); pure concentration gradient driven diffusion, aided by the temperature decline forms a powerful pump to deplete the surface layers of CO2 and drive it deeper.

    Now if the surface temperatures should rise; we would expect outgassing from the surface to put more CO2 in the atmosphere; BUT1 if the surface layers are somewhat depleted by diffusion, then there isn’t a whole host of CO2 available to supply that outgassing.
    I think that is why a general warming doesn’t result in an immediate CO2 increase in the atmosphere; because the CO2 excess has been moved to deeper waters; and it is going to take actual water circulation to bring that reservoir of CO2 back to where it can be exchanged with the atmosphere.

    The process seems to me to be somewhat analagous (but different) from the charge depletion that occurs at a semiconductor junction interface to form a depletion region at the interface.

    So the data you show Willis, just doesn’t surprise me at all. In fact it is kind of comforting to see that Mother Gaia seems to like to follow the rules, and move her CO2 around the way ity was intended.

    And when you see the 18 ppm P-P annual cycle in the Atmospheric Arctic CO2 abundance, compared to 6 ppm at Mauna Loa, and about a negative 1 ppm (out of phase) cycle at the south pole; it seems like everything just fits into place.

    I had to laugh at Jane Lubchenko’s big public demonstration of ocean acidification, that she performed on camera.

    Seems that Jane (I think she’s an oceanographer) took some “ordinary tap water” and dyed it with “an ordinary laboratory blue dye” ( I think the brand name of the dye was “phenolphthalene”; I prefer the “Litm,us” brand myself); and she then chilled the ordinary tap water with about a pound or two of dry ice, that she dumped into the water; and the ordinary laboratory blue dye turned into an ordinary laboratory yellow dye, therby proving that corals and shell fish can thrive in ordinary tap water with its chlorine and fluoride etc, so long as you dye it blue with an ordinary laboratory blue dye; but if you chill it and paint it yellow instead, then the corals presumably won’t grow in ordinary tap water.

    Way to go Jane; some experimentalist you are. So why didn’t you start with some “ordinary oceanic sea water” say from the Great barrier reef for example; where it is believed that corals and shellfish can grow; and then try dyeing that blue with your ordinary laboratory blue dye; why didn’t you do that Jane ??

    I think we are all concerned about pollution of the oceans; and the rape of the fisheries, and other abuses; but the natural uptake of CO2 by the oceans is not one of the top things on my list of oceanic concerns.

  111. CO2 Says

    I should have added, “Because of other factors”, a warmer ocean…
    Ocean acidity is not only a simple function of CO2 disolving in water, it involves the bio-mass from Phyto-plankton and Zooplankton down, which sequester CO2 drawing on the disolved CO2 carrying it to both the deep waters and the ocean floor. This is referred to as the solubility pump and the biological pump. This bio-mass of Phytoplankton and Zooplankton, residing close to the surface, is threatened by the warming of colder oceans, resulting in less absorbtion of CO2, increasing the disolved CO2 level, hence acidity. The whole issue is far more complex than a discussion about Ph, acidity and alkaline. While a warmer ocean may absorb less CO2, the CO2 level will still increase if the rate of sequestration drops disproportionally.

    There are 3 pumps eg

    Volk and Hoffert [1985] define an ocean carbon pump
    as ‘‘a process that depletes the ocean surface of dissolved
    inorganic carbon (DIC) relative to the deep-water DIC.’’
    They recognized three such pumps: the soft-tissue pump, the
    carbonate pump and the solubility pump. While the first two
    are biological, the third is a response to solubility differences
    of CO2 in warm and cold water

    The soft pump raises significant constraints to a number of spurious arguments eg Marinov et al 2008

    [1] We use both theory and ocean biogeochemistry models to examine the role of the
    soft-tissue biological pump in controlling atmospheric CO2. We demonstrate that
    atmospheric CO2 can be simply related to the amount of inorganic carbon stored in the ocean by the soft-tissue pump, which we term (OCSsoft). OCSsoft is linearly related to the inventory of remineralized nutrient, which in turn is just the total nutrient inventory minus the preformed nutrient inventory. In a system where total nutrient is conserved, atmospheric CO2 can thus be simply related to the global inventory of preformed nutrient. Previous model simulations have explored how changes in the surface concentration of nutrients in deepwater formation regions change the global preformed nutrient inventory. We show that changes in physical forcing such as winds, vertical mixing, and lateral mixing can shift the balance of deepwater formation between the North Atlantic (where preformed nutrients are low) and the Southern Ocean (where they are high). Such changes in physical forcing can thus drive large changes in atmospheric CO2, even with minimal changes in surface nutrient concentration. If Southern Ocean deepwater formation strengthens, the preformed nutrient inventory and thus atmospheric CO2 increase. An important consequence of these new insights is that the relationship between surface nutrient concentrations, biological export production, and atmospheric CO2 is more complex than previously predicted. Contrary to conventional wisdom, we show that OCSsoft can increase and atmospheric CO2 decrease, while surface nutrients show minimal change and export production decreases.

  112. toho (June 20, 2010 at 8:40 am)
    Thanks for that. Kind of confirmed my suspicions.

    It did occur to me too that the even the act of filtering, heating and pumping the water into (large) aquarium tanks could cause pH changes of the magnitude decribed in the post (simply because the natural variation that is so “worrying” is so small).

  113. I come back to several earlier comments. The claims of this paper are dependent on new spectrophotometric technology claiming some remarkable field precision for pH measurement -the patents of the method and instrument being those of the author of the paper in question. Given the precision and accuracy of conventional equipment no such claims for a CO2 signature could be made- as the claims do not rise above instrument and method noise.)
    This is important for a number of reasons but my biggest concern is that it implies no historical pH data set can be used to argue with conclusions made by spectrophotometric measurements. Will we also see “adjustments” of the historical pH records– it certainly worked for temperature?

  114. CO2 says:
    June 20, 2010 at 3:51 am

    Chris says:
    June 20, 2010 at 2:15 am
    Great post, I made a start on something similar, but you’ve done it far, far better and saved me a lot of research, many thanks. This is a red herring, a desperate diversion from the evolving situation in the arctic. I’m awaiting the results from the last Catlin survey.

    And the sad part is, you appear to mean that seriously about the Catlin survey

    And a “desperate diversion” from the Arctic? Dude, I write about what interests me. I have written about the Arctic many times, and likely will again. I’m not trying to divert anyone from anything, it’s all fascinating learning opportunities for me.

    For example, my guess is that you didn’t know that the Monterey Bay water changed pH so fast, or that there was a large difference between Hawaiian and Alaskan water. I’m a reformed cowboy, not a sophisticate, so I can say “I was surprised by …” or “I learned a lot from …”

    You ought to try it, it’s kinda fun to learn new things.

  115. chris y says:
    June 20, 2010 at 5:19 am

    Willis, another thought on this paper. Rainwater has a pH that ranges from 4.5 – 5.5. It seems to me that the entire variation measured in the paper (particularly the changes in pH near the surface) could be caused by small changes in precipitation rates along the chosen transect, between the two sampling times. In other words, natural variability in local ocean pH, driven partly by precipitation dynamics over monthly, annual and decadal timescales, is being woefully under-sampled in this study.

    Yeah, I was wondering that as well … but like I said, I accepted their conclusions purely for the sake of the discussion, to show that even if true they were trivially small.

  116. Dave Springer says:
    June 20, 2010 at 6:54 am

    Willis,

    What makes you say the pH change is human-induced? Jump to conclusions much?

    I do not jump to conclusions much. I have accepted the authors’ claims at face value for the sake of argument only. I don’t know if they are right or wrong in their measurements and their assumptions.

  117. Chris says:
    June 20, 2010 at 2:15 am

    Quotes from this blog post are in bold and my responses follow.

    Heck, even the name “acidification” is alarmist, because sea water is not acid, nor will it every be. What we are seeing is a slight reduction in how alkaline the sea water is.

    Acidification is the act of adding an acid to a solution, it has nothing to do with whether the solution is acidic or basic (i.e., basic, neutral, and acidic solutions can all be acidified by adding an acid to them). CO2 in water forms carbonic acid, so adding CO2 to the ocean is, well, ocean acidification.

    That’s its denotation, but its connotation is that it’s turning into lemon juice. I suggest putting the word inside quotation marks, as a signal that it mustn’t be taken as meaning “becoming sour (acid).” Or, better, how about “ocean neutralization”? The denotation isn’t as precise, but the connotation isn’t misleading. The trade-off is worth it.

    It’s not alarmist, it’s simply grammar.

    Grammar and usage have many subsurface booby-traps (exceptions, and exceptions to the exceptions), counter-intuitive rules, and nuances. It can get quite tricky. Incidentally, a very readable and concentrated book on such matters is Woe Is I, available here:

  118. The correct jargon is as follows:

    a) When you add an acid to a substance, it is “acidulation.” Acidulation is commonly used in refinery wastewater treatment to crack oil/water emulsions. We typically use concentrated sulfuric acid for this.

    b) When a liquid becomes more acidic via natural or deliberate process, it is “acidification.” The first phase of Dr. Sam Ghosh’s split-phase anaerobic treatment system is called the “acidification” step, as the facultative microbes are converting short-chain organic molecules into various acids (primarily acetic).

    I think the absolutely accurate term would be “oceanic acidification.”

  119. Ocean ventilation is essential to understanding near surface pH. Chris has posted in response to Willis that ocean circulation is on the order of ~ 1000 years. The ocean acidification models agree and as such do not assume any mixing of surface water in their calculation of the 100 year surface pH projections. So is this correct?

    Just read an interesting caution by a retired Argonne employee Gerald Marsh “Seawater pH and Anthropogenic CO2″. http://www.gemarsh.com/…/SEAWATER%20pH%20&%20ANTHRO%20CO2%20V2.pdf He cites a study byJenkins and Smethie, Jr. who used tritium (A bomb test residue) to look at ocean ventilation time scales. Tritium has mixed down some 500 to 1000meters in the Atlantic subtropics, 1500 to 2000 m off New England (south of Gulf stream)
    and north of the Gulf Stream extension is at the ocean floor!!! They also found tritium off Bermuda had descended a thousand meters in a decade (1970s to 80s)

    Byrne et al. seems to allow for minimal mixing (approx 0.01ph units) based on a slow down in recent ocean mixing -which in turn is based on a MODEL. If there was mixing one could not ascribe anything to CO2 as the pH differential is almost 0.7 units in the top 1000m along their transect.

    So ocean mixing seems to be occurring much more than allowed for in the acidification models. Any bets on how much grant money will be available to validate the respiration and ventilation rate assumptions made in the ocean acidification models?

  120. DirkH says:
    June 20, 2010 at 6:13 am

    “BTW who are “the thousands of scientists ” and why do you carry that silly number around with you as if it means something? Are you that easily impressed? Where do you have that number from?”
    =====

    It is interesting to note that no less a luminary than Mike “the idea of climate change is so plastic” Hulme has recently “debunked” a variant of the “thousands of scientists” consensus myth:

    Honey, I shrunk the consensus!

  121. PAEH says:
    June 20, 2010 at 8:37 am
    Phil. says:
    June 19, 2010 at 10:33 pm

    flyfisher says:
    June 19, 2010 at 8:53 pm
    One other thing to consider: what is the standard error of their equipment? I’d be astounded if their measurement device was accurate below 0.01 pH Units.

    Perhaps you should have read the paper (specifically Data and Methods):

    “Measurement precision on both transects was on the order of ±0.001″

    Phil,

    give up now, you obviously have no knowledge of what you are demanding that everyone else accepts without question.

    pH CANNOT be measured to 0.001 units. The buffer solutions used to calibrate electrodes are only accurate to +/- 0.1 pH units, and that is recognized in international standards.

    If you look at the sentence you pulled from that paper, it would seem to refer to location, i.e. longitude and latitude

    No you’re wrong again, you should have taken my advice and read the paper! I’ve included the whole paragraph which makes it clear that it is pH measurement that is being described. Also note that it’s a spectrophotometric method that’s used not an electrode method.

    “2. Data and Methods

    [5] Precise spectrophotometric procedures for seawater pH measurement were developed between 1985 and 1993 [Robert-Baldo et al., 1985; Clayton and Byrne, 1993], and the first successful application on an ocean expedition occurred in March 1991 (WOCE P16N; 750 pH samples) along a cruise transect between Oahu, Hawaii, and Kodiak, Alaska (Figure 1). This transect was reoccupied in March 2006 (CLIVAR/CO2 Repeat Hydrography Program P16N; 1356 pH samples). Both datasets, obtained at 25°C and reported on the total hydrogen ion concentration scale (pHT = −log[H+]T), are available from the CLIVAR & Carbon Hydrographic Data Office (CCHDO, http://cchdo.ucsd.edu/pacific.html). The spectrophotometric method [Clayton and Byrne, 1993] relies on molecular properties of the pH indicator meta-cresol purple. A small amount of dye ([mCP] ~ 3 μM) was added to each sample, and absorbance was measured at 434 and 578 nm and at a non-absorbing wavelength, against a reference solution of pure seawater. Directly measured pH, pHm, was then calculated from absorbance ratios. These data were collected before the practice of purifying indicators was adopted, so a correction for mCP impurities was applied to the 2006 pH data: 0.001 units at pH 7.4, increasing to 0.005 at pH 8.1 [Yao et al., 2007]. Measurement precision on both transects was on the order of ±0.001 (somewhat smaller than the annual pH change expected for seawater in equilibrium with the atmosphere).”

  122. Why is a decrease in alkalinity called “acidification”? I suggest it’s because “debasement” already has a definition, and it would sound really weird in this context.

  123. Jimbo!

    You earlier asked for Essenbach or anyone better qualified than you to look at something.

    [~SNIP~ Deliberately insulting someone who devotes a lot of time writing popular articles for the readers of this site didn’t get by this moderator. ~dbs]

  124. Phil:
    How about the precision of ventilation and respiration rates that are required to define the AGW signature? Do you think we know these well enough to claim an AGW pH decline of a few hundredths a pH unit?

    Here is a good test– lets give the authors on some future cruise along the same transect- alkalinity, salinity, temperature, DOC, and air CO2 etc and have them predict before sampling the pH within the limits ascribed by their paper to AGW CO2. Basically their paper is saying they know what the ocean pH is supposed to be. I say prove it!

  125. Your update re what organisms can cope with doesn’t answer it. Yes, in their current environments they are subjected to a range of pHs and they cope with that. But acidification (sorry, reduced alkalinity) shifts the mean, so most likely it shifts the extremes correspondingly. Furthermore, they might be able to cope with transient excursions outside their comfort range but not a sustained shift.

    Wrt predictions, both your numbers and the ones I referred you to (e.g. http://web.archive.org/web/20080625100559/http://www.ipsl.jussieu.fr/~jomce/acidification/paper/Orr_OnlineNature04095.pdf) are calculations, assuming a model, and based on observations. Their model and calculations are the far more impressively detailed, but yours use more recent data. I eagerly await a peer-reviewed published paper based on these latest numbers.

  126. flyfisher wrote:
    > One other thing to consider: what is the standard error of their
    > equipment? I’d be astounded if their measurement device was
    > accurate below 0.01 pH Units.

    If you’d read the paper you’d find out: “Measurement precision on both transects was on the order of ±0.001 (somewhat smaller than the annual pH change expected for seawater in equilibrium with the atmosphere).” (paragraph 5)

  127. DerekB
    How about before we go spending a whole bunch of money on what flora and fauna can or cannot survive we make sure we understand this is a real issue.
    But how do we get a peer reviewed study without grants and who is going to fund anything that may challenge ocean acidification?
    The last time we studied acidification was the 80′s which culminated in the Acid Rain study -NAPAP. The interim report was not up to alarmist standards so the the head of NAPAP was forced to step down. The new head of NAPAP was forced to promise Congress that they would not find that acid rain wasn’t as bad as claimed. They couldn’t so- EPA refused to release the report. The lead scientist ED Krug went on 60 minutes to speak against these actions- EPA slandered and blacklisted him as a result.
    I lost trust in this system a long time ago.

  128. Derek B,

    Your link is broken, so I’ll accept what you’ve written above. I should point out that the Monterey Bay Aquarium takes actual pH measurements at the inlet. The aquarium pumps in ocean water from well out in the bay and runs it through the tank and back out again, so it is not a calculated model. Those are real world pH measurements.

    I used to raise tropical fish for many years in community tanks up to 125 gallons. Different fish species prefer different pH, and the preference range is wide, from about 6.5 – 8.5.

    Despite that wide range, my fish all thrived in a pH of 7 – 7.5. Why? Because pH is probably the least important water parameter. Temperature, salinity, nitrates, nitrites, etc., all have a much bigger effect on fish. I’ve never had a reef [saltwater] aquarium, but I suspect that pH is likewise much less critical than other factors. Maybe someone with reef tank experience could comment. Reef tanks use live sand and corals, so it might be a different situation wrt pH.

  129. Interesting that the alkilinity follows the temperature record (SST), this and the drop in alkalinity towards cooler climes shows that the sea is cycling c02 quite rapidly. In 1998 when we had a sudden El Nino spurt of warming, we sea the co2 growth rate at Mauna Loa increase, and at the same time sea alkalinity increases – this supports that part of the rise in co2 being observed is from the sea. Also as the sea cools, it begins to absorb co2 and the alkilinity decreases. All interesting stuff.

  130. Once again, we here the precision of 0.001. And yet…

    “These data were collected before the practice of purifying indicators was adopted, so a correction for mCP impurities was applied to the 2006 pH data: 0.001 units at pH 7.4, increasing to 0.005 at pH 8.1 [Yao et al., 2007]. ”

    So the corrections are greater than the precision?

    It would be nice if the paper actually gave details on how the precision was determined, with perhaps some sample data showing the spread.

    I return to the paper I linked to, which was published later than the papers that this paper cites in the methods section, and reports a cruise-to-cruise 1 sigma of 0.0032 pH units.

    http://wattsupwiththat.com/2010/06/19/the-electric-oceanic-acid-test/#comment-413320

  131. John M- And I don’t think the problems with the “early” indicators allowed so simple a correction. There were issues with impurities on a batch to batch basis.

  132. Fraizer says:
    June 19, 2010 at 7:33 pm

    A couple of questions for our alarmist friends:

    1) What is the ultimate carrying capacity of an infinitely buffered alkaline solution for an acid gas?

    2) Where does limestone come from?
    ———————
    No fair. You should at least give us the answers upside down at the bottom.

  133. John M says:
    June 20, 2010 at 5:59 pm
    Once again, we here the precision of 0.001. And yet…

    “These data were collected before the practice of purifying indicators was adopted, so a correction for mCP impurities was applied to the 2006 pH data: 0.001 units at pH 7.4, increasing to 0.005 at pH 8.1 [Yao et al., 2007]. ”

    So the corrections are greater than the precision?

    That’s frequently the case, that’s why we do calibrations, you do know what precision means don’t you?

  134. Caleb- Funding was passed as the Foaram Act “The Federal Ocean Acidification Research and Monitoring ” in 2009. The Act authorizes appropriations for ocean acidification research for fiscal years 2009, 2010, 2011, and 2012, at $14 million, $20 million, and $27 million, and $35 million per year. (And more are in line)

    The Foaram Act assumes the reality of ocean acidification. Grants are available to assess the impacts of ocean acidification. Congress has like all environmental laws before it ruled on the science at the lobbying of the NGOs and then academia is paid to justify the ruling. There will be no debate on ocean acidification.

  135. A lot has been written, asked, etc. since my post above. Since it would require quite a bit of writing to answer every point and, well, I’ve got a day job ;-) I’ll address Willis’ posts specifically, since he is the author of the post.

    Chris, you are grasping at straws. As I said above, the point is that it is alarmist terminology. It leads people who think the ocean is neutral to be fearful that the ocean is turning into an acid.

    Willis, I simply responded to the point you raised. You said that the term “ocean acidification” is incorrect and alarmist. As I said, I think it’s a bit silly to quibble over accepted terminology (e.g., complaining that sea horses aren’t actually horses) on the one hand, and on the other the point you made is simply wrong. Ocean acidification is in fact acidification. The usage is correct. It is also the widely accepted name for this process. If you don’t like the term and want to use another one you can, but complaining about it, just like complaining that people call sea horses “horses” is, to me, silly and just plain a waste of time, effort, and html ;-)

    This, and your long, long list of nitpicks above (yes, 7.0 is only neutral in pure water at 25°C, and in the ocean it’s about 6.9 … so what?) are generally technically correct and totally meaningless.

    That is exactly the point though, isn’t it. As I said above, I wouldn’t nit pick here except that you were (incorrectly) nit picking the term ‘acidification.’ You pick: either we’re nit picking terminology or we’re not. If you don’t want to nit pick over terms when it is uncritical to the discussion, then don’t do so.

    The point is simple. The change in oceanic basicity is so small and so slow that it will not affect much of anything.

    You’re simply asserting it doesn’t matter based on no evidence whatsoever. In fact much of the experimental data demonstrates that acidification along the lines of what we’re on track to see this century has a number of negative consequences for many organisms. The data show quite explicitly that, in fact, it does affect quite a lot.

    In many places, including coral reefs, the ocean sees larger pH changes daily than the total change projected from changing CO2 over the next century.

    That’s a red herring: the fact that some marine environments (e.g., many coral reefs) experience substantial daily pH variation around the average does not mean that shifting the average pH lower will have no effect. A lagoon might see daily pH variation from 7.8 to 8.8 with a mean of 8.1. Shifting the entire range down to an average pH of 7.7 will get you a range of 7.5 to 8.5. Sure enough, the experimental data suggests that a lot of reef organisms (many corals, coralline algae, etc.) experience negative consequences from this shift.

    Daily, seasonal, and interannual variation in pH are superimposed on the mean. Reducing the mean doesn’t necessarily affect the variability, it shifts the entire pH range down.

    You say that:
    There is one misconception of yours I do want to clear up, however. You say:
    In response to:
    No, all of the values above assume that there WILL be mixing. If there were no mixing then the reduction in surface ocean pH would be much larger than those I’ve mentioned above.
    And respond that:
    You speak in hushed tones about how

    All the projections of changes in surface ocean pH, for instance those by Caldeira, Zeebe, and others, assume mixing, both within the surface layer and between the surface and deep sea. If there were no mixing then the only process transporting CO2 into the ocean would be diffusion, and diffusion is incredibly slow over larger distances (meters+). If there were no mixing then the CO2 released to the atmosphere would only be taken up by the very surface layer of the ocean (diffusional boundary layer), which would absorb a very small fraction of the CO2 emitted input because the layer is so thin. Thus the atmospheric concentration would be much higher because so little of the CO2 would be taken up by the ocean, and the surface layer in direct contact with this high CO2 concentration would experience a much larger decline in pH.
    Without mixing the pH decline at the surface would be much larger and would penetrate into the ocean extraordinarily slowly. All projections include oceanic mixing.

    According to the references I’ve seen, if the atmospheric CO2 were to double instantaneously, the oceanic surface pH would go down by about 0.26, not 0.4.
    We’re on track to have doubled preindustrial CO2 (560 uatm) by around mid-century, which would indeed get you about a 0.25 decrease in surface pH (we’ve already had about 0.1 of that). We are on track to see a >0.4 unit decline in pH by 2100, when atmospheric CO2 will be much higher than 560 uatm (on track for >800 uatm).

    This is much less than a month’s pH change in the Monterey Bay seawater. But the extra CO2 in the surface would eventually mix throughout the ocean, reducing the atmospheric CO2 and increasing the surface basicity (your preferred term).

    Just as above, this is a red herring. Monthly variability in instantaneous pH in Monterrey Bay (or any other location) does not in any way counteract the decline in mean pH. Instead of varying from ~7.8-8.1 with a mean near 7.95 we’d see something more like a range of ~7.5-7.9 with a mean near 7.75.

    Over long time scales pH at the surface will rise due in part to oceanic mixing (and redistrubution of the slug of CO2 at the surface) and weathering processes consuming the CO2. However, the decline in pH we’re talking about occurs ASSUMING that oceanic mixing and weathering are occuring the entire time. Over shorter time scales, on the order of a century, oceanic mixing can only moderate the CO2 input so much because a mixing cycle takes on the order of 1000 yrs. Weathering, especially silicate weathering, is much slower still. Yes, eventually the CO2 input will be redistributed by physical processes, and sequestered by geological ones, but all of those effects are very small until long, long after you, me, our kids, grandkids, etc. are long dead.
    Geologic data suggests that similarly large CO2 input in the past (e.g., work by Zachos on the PETM) takes tens of thousands of years to dissipate. In 100,000 yrs oceanic chemistry will be pretty well getting back to normal but, well, I’m kinda interested in these next 100,000 yrs (an less).

    Yeah, I was wondering that as well … but like I said, I accepted their conclusions purely for the sake of the discussion, to show that even if true they were trivially small.

    The above is in response to a suggestion that rainwater input (since rain has a pH of ~4-5) can substantially affect seawater pH. pH is not a conservative property of solutions. Mixing a solution of pH 4 with a solution of pH 8 in equal amounts doesn’t get you a pH of 6. The resultant pH depends on what was in each solution. Mixing rainwater (pH 4.5) with sea water (pH 8.1) in equal amounts will get you a pH of about 7.9. Rainwater has one important effect on seawater pH and that is that rain dilutes seawater, thereby diluting the total alkalinity. The salinity, and therefore total alkalinity, is higher in the subtropics than equatorial and polar regions because evaporation exceeds rainfall there. Hence, pH tends to be a bit higher, but the effect is relatively small (0.03 for a reduction in salinity from 35 to 32 ppt). Regardless, this effect is wholly unimportant in creating a trend of reduced pH across latitudes, at about constant salinity at a given site.

    Best,

    Chris

  136. Referring to the French paper I cited:

    “Ocean uptake of CO2 will help moderate future climate change, but the associated chemistry, namely hydrolysis of CO2 in seawater, increases the hydrogen ion concentration [H+]. Surface ocean pH is already 0.1 unit lower than preindustrial values.

    By the end of the century, it will become another 0.3–0.4 units lower under the IS92a scenario, which translates to a 100–150% increase in [H+].

    Simultaneously, aqueous CO2 concentrations [CO2(aq)] will increase and
    carbonate ion concentrations ½CO223  will decrease, making it more
    difficult for marine calcifying organisms to form biogenic calcium carbonate (CaCO3). Substantial experimental evidence indicates that calcification rates will decrease in low-latitude corals, which form reefs out of aragonite, and in phytoplankton that form their tests (shells) out of calcite, the stable form of CaCO3.”

    http://www.up.ethz.ch/education/biogeochem_cycles/reading_list/orr_nat_05.pdf

    Quite honestly, acidification of the ocean liquid/atmosphere interface is the only phenomenon that matters, as nearly all oceanic photosynthesis occurs quite close to this surface boundary. The concern I have is for the phytoplankton that are dependent upon calcification, as the higher carbon dioxide seems to mess with the production of aragonite & calcite.

    This is the only aspect of AGW that I can see giving any creedence to (acidification of photosynthetic boundary).

    BTW, Willis, I have also worked in commercial fishing out of Gloucester, Mass, Pt. Judith RI & other places.

  137. CRS, Dr.P.H. says:
    June 20, 2010 at 9:18 pm

    Thanks, CRS. You say:

    Referring to the French paper I cited:

    “Ocean uptake of CO2 will help moderate future climate change, but the associated chemistry, namely hydrolysis of CO2 in seawater, increases the hydrogen ion concentration [H+]. Surface ocean pH is already 0.1 unit lower than preindustrial values.

    By the end of the century, it will become another 0.3–0.4 units lower under the IS92a scenario, which translates to a 100–150% increase in [H+].

    Referring to the French paper you cited:

    Here we use 13 models of the ocean–carbon cycle to assess calcium carbonate saturation under the IS92a ‘business-as-usual’ scenario for future emissions of anthropogenic carbon dioxide.

    As far as I know, we have absolutely no evidence that models can forecast calcium carbonate saturation in the ocean. If you know of any models whose results have actually been tested in that regard, please let us know.

    They also have a nasty habit of making uncited assertions. For example, they say:

    Surface ocean pH is already 0.1 unit lower than preindustrial values.

    How do they know that? They don’t say. As far as I know, there is no global dataset of the “surface ocean pH”. As the Monterey Aquarium figures show, it can vary by half a unit in a month … and they want us to believe that not only do we know the average surface ocean pH today to within a 95% CI of ±.05 units, they also know the pre-industrial surface ocean pH to within the same accuracy? … riiiight …

    Next, they say:

    By the end of the century, [pH] will become another 0.3–0.4 units lower [1,2] under the IS92a scenario, which translates to a 100–150% increase in [H+].

    But reference 1 doesn’t say that. It says:

    … a further reduction of 0.2 to 0.3 pH units may occur in the next century.

    And I suspect that the reference 2 is in error. It is a paper on the effect of CO2 on haline concentration in the ocean.

    So let’s consider this French paper. Based on models, unreferenced and highly improbable claim of great accuracy in the pre-industrial signal, one reference gives different numbers from those they cite, another reference is likely bad … so as far as I’m concerned, those guys are just blowing smoke. It should have never made it through peer-review process with those kind of claims, but we all know how rigorous that process is.

    If what they say is true, and the global oceanic PH has changed by 0.1 units since pre-industrial times, and the ocean is as sensitive to pH changes as folks say … why haven’t we seen the effects of that?

    The main problem that I have with all of these oceanic chemistry models and calculations is that they ignore the fact that the ocean is not just a bath of chemicals. It is full top to bottom and brimming over with life.

    And life has a nasty habit of driving chemical reactions in all kinds of directions, including the opposite direction of how the reaction might go in a simple bath of chemicals. Simple chemistry would never show that the pH of the water around coral reefs is greater during the day and lower during the night, and is generally lower overall than the surrounding water … but it is. Why? Because coral respires CO2, and is actually a net source of CO2 to the atmosphere.

    And there’s not a climate model in the world that includes that, or a thousand other life-driven chemical reactions in the ocean.

  138. Derek B says:
    June 20, 2010 at 5:06 pm

    Your update re what organisms can cope with doesn’t answer it. Yes, in their current environments they are subjected to a range of pHs and they cope with that. But acidification (sorry, reduced alkalinity) shifts the mean, so most likely it shifts the extremes correspondingly. Furthermore, they might be able to cope with transient excursions outside their comfort range but not a sustained shift.

    Derek, that is certainly possible. However, the only measurement that we have is the Bryne paper, which shows a change in pH of about .001 units per year. I’m sorry, but I’m not going to get concerned about that. The Monterey Bay measurements show changes a hundred times that large in less than a month …

    In a hundred years, it might (and I emphasize the might) make a change of 0.1 units. Theoretically, we’ve already seen that much change in the last two hundred years … perhaps you could point to the deleterious effects caused by that change?

    If you want to be concerned about that, it’s your choice. I prefer to worry about things for which we have actual evidence …

  139. Chris-You state “Without mixing the pH decline at the surface would be much larger and would penetrate into the ocean extraordinarily slowly. All projections include oceanic mixing.”
    How confident are you about the state of our knowledge of ocean mixing such that we can extract a few hundredths of of pH unit AGW signature?

    I do agree with your comment on the minimal impact of rain on mid ocean pH.

  140. Chris says:
    June 20, 2010 at 9:01 pm

    A lot has been written, asked, etc. since my post above. Since it would require quite a bit of writing to answer every point and, well, I’ve got a day job ;-) I’ll address Willis’ posts specifically, since he is the author of the post.

    Chris, you are grasping at straws. As I said above, the point is that it is alarmist terminology. It leads people who think the ocean is neutral to be fearful that the ocean is turning into an acid.

    Willis, I simply responded to the point you raised. You said that the term “ocean acidification” is incorrect and alarmist. As I said, I think it’s a bit silly to quibble over accepted terminology (e.g., complaining that sea horses aren’t actually horses) on the one hand, and on the other the point you made is simply wrong. Ocean acidification is in fact acidification. The usage is correct. It is also the widely accepted name for this process. If you don’t like the term and want to use another one you can, but complaining about it, just like complaining that people call sea horses “horses” is, to me, silly and just plain a waste of time, effort, and html ;-)

    OK, I get it. You don’t think alarmist terms are worth discussing. But people respond to the emotional content of terms. I think that’s important. I could call people who support the AGW hypothesis “sheeple”, and they could call me a “denier”. I don’t call them “sheeple”, because the emotional content of the terms I use is important to me. They continue to call me a “denier”, despite the unpleasant emotional connotations …

    This, and your long, long list of nitpicks above (yes, 7.0 is only neutral in pure water at 25°C, and in the ocean it’s about 6.9 … so what?) are generally technically correct and totally meaningless.

    That is exactly the point though, isn’t it. As I said above, I wouldn’t nit pick here except that you were (incorrectly) nit picking the term ‘acidification.’ You pick: either we’re nit picking terminology or we’re not. If you don’t want to nit pick over terms when it is uncritical to the discussion, then don’t do so.

    I am not “nit-picking”. I am talking about the emotional content of the terms we use to describe something. It is not irrelevant that you don’t think this is important.

    The point is simple. The change in oceanic basicity is so small and so slow that it will not affect much of anything.

    You’re simply asserting it doesn’t matter based on no evidence whatsoever. In fact much of the experimental data demonstrates that acidification along the lines of what we’re on track to see this century has a number of negative consequences for many organisms. The data show quite explicitly that, in fact, it does affect quite a lot.

    A citation to an experiment showing that a change in pH of 0.001 units per year has “negative consequences” would be useful to your argument. In the absence of such a claim, it doesn’t make much sense. If, and it’s a big if, this causes a change in the oceanic pH of 0.1 units over the next century, that is not a large change compared to the daily, monthly, and annual changes we see in the ocean.

    In many places, including coral reefs, the ocean sees larger pH changes daily than the total change projected from changing CO2 over the next century.

    That’s a red herring: the fact that some marine environments (e.g., many coral reefs) experience substantial daily pH variation around the average does not mean that shifting the average pH lower will have no effect. A lagoon might see daily pH variation from 7.8 to 8.8 with a mean of 8.1. Shifting the entire range down to an average pH of 7.7 will get you a range of 7.5 to 8.5. Sure enough, the experimental data suggests that a lot of reef organisms (many corals, coralline algae, etc.) experience negative consequences from this shift.

    Chris, you are just picking numbers. You assume that there will be a shift of 0.4 units. The evidence we have to date (the Bryne paper) shows that we may get a shift of 0.1 units in a hundred years. If the rate double, we may get 0.2 units. Stick with the evidence. Also, saying “the experimental data suggests” means nothing. I’ve provided citations. Your turn. Give us a citation of the damage from a change in pH of 0.1 – 0.2 units …

    Daily, seasonal, and interannual variation in pH are superimposed on the mean. Reducing the mean doesn’t necessarily affect the variability, it shifts the entire pH range down.

    You are assuming that there is no shift in what you are calling “the mean”. We have no evidence that that is the case. There are likely variations over longer periods as well. It is clear that the El Nino has an effect. It is likely that the PDO has an effect. And the general warming since the Little Ice Age will have had an effect.

    You say that:

    There is one misconception of yours I do want to clear up, however. You say:
    In response to:
    No, all of the values above assume that there WILL be mixing. If there were no mixing then the reduction in surface ocean pH would be much larger than those I’ve mentioned above.
    And respond that:

    You speak in hushed tones about how

    All the projections of changes in surface ocean pH, for instance those by Caldeira, Zeebe, and others, assume mixing, both within the surface layer and between the surface and deep sea. If there were no mixing then the only process transporting CO2 into the ocean would be diffusion, and diffusion is incredibly slow over larger distances (meters+). If there were no mixing then the CO2 released to the atmosphere would only be taken up by the very surface layer of the ocean (diffusional boundary layer), which would absorb a very small fraction of the CO2 emitted input because the layer is so thin. Thus the atmospheric concentration would be much higher because so little of the CO2 would be taken up by the ocean, and the surface layer in direct contact with this high CO2 concentration would experience a much larger decline in pH.
    Without mixing the pH decline at the surface would be much larger and would penetrate into the ocean extraordinarily slowly. All projections include oceanic mixing.

    Mixing in the ocean is very poorly understood. The Caldeira paper uses a very simplistic model. I suspect that this is one reason why the Bryne results show much smaller changes than the models.

    According to the references I’ve seen, if the atmospheric CO2 were to double instantaneously, the oceanic surface pH would go down by about 0.26, not 0.4.

    We’re on track to have doubled preindustrial CO2 (560 uatm) by around mid-century, which would indeed get you about a 0.25 decrease in surface pH (we’ve already had about 0.1 of that). We are on track to see a >0.4 unit decline in pH by 2100, when atmospheric CO2 will be much higher than 560 uatm (on track for >800 uatm).

    The problem is that the ocean is full of life. The net result is that theoretical chemical calculations don’t work. This is an example.

    During the fifteen year period of the Bryne study (1991-2006), the CO2 went up by 26.4 ppmv. The pH went up by about 0.02 units. This is a change in pH of .0005/ppmv CO2. And this in turn means that if the atmospheric CO2 were to go up to 800 ppmv (about a 415 ppmv increase), pH would be expected to go up by about 0.2 units …

    This is much less than a month’s pH change in the Monterey Bay seawater. But the extra CO2 in the surface would eventually mix throughout the ocean, reducing the atmospheric CO2 and increasing the surface basicity (your preferred term).

    Just as above, this is a red herring. Monthly variability in instantaneous pH in Monterrey Bay (or any other location) does not in any way counteract the decline in mean pH. Instead of varying from ~7.8-8.1 with a mean near 7.95 we’d see something more like a range of ~7.5-7.9 with a mean near 7.75.

    As I said, you’ll have to show that that would be an issue. Me, I don’t think that the change in atmospheric CO2 will be as large as the IPCC says, nor do I think that a change in CO2 of 0.2 ppmv (if it were to happen over the next hundred years) will be an issue. Theoretical IPCC calculations say we’ve already seen half of that change (0.1 units) … where is the damage from that?

    Over long time scales pH at the surface will rise due in part to oceanic mixing (and redistrubution of the slug of CO2 at the surface) and weathering processes consuming the CO2. However, the decline in pH we’re talking about occurs ASSUMING that oceanic mixing and weathering are occuring the entire time. Over shorter time scales, on the order of a century, oceanic mixing can only moderate the CO2 input so much because a mixing cycle takes on the order of 1000 yrs. Weathering, especially silicate weathering, is much slower still. Yes, eventually the CO2 input will be redistributed by physical processes, and sequestered by geological ones, but all of those effects are very small until long, long after you, me, our kids, grandkids, etc. are long dead.
    Geologic data suggests that similarly large CO2 input in the past (e.g., work by Zachos on the PETM) takes tens of thousands of years to dissipate. In 100,000 yrs oceanic chemistry will be pretty well getting back to normal but, well, I’m kinda interested in these next 100,000 yrs (an less).

    The mixing in the oceans takes place faster than simple models assume. This is because of life and its myriad processes. But in any case, Bryne results show that the changes we are likely to see will be quite small.

    Yeah, I was wondering that as well … but like I said, I accepted their conclusions purely for the sake of the discussion, to show that even if true they were trivially small.

    The above is in response to a suggestion that rainwater input (since rain has a pH of ~4-5) can substantially affect seawater pH. pH is not a conservative property of solutions. Mixing a solution of pH 4 with a solution of pH 8 in equal amounts doesn’t get you a pH of 6. The resultant pH depends on what was in each solution. Mixing rainwater (pH 4.5) with sea water (pH 8.1) in equal amounts will get you a pH of about 7.9. Rainwater has one important effect on seawater pH and that is that rain dilutes seawater, thereby diluting the total alkalinity. The salinity, and therefore total alkalinity, is higher in the subtropics than equatorial and polar regions because evaporation exceeds rainfall there. Hence, pH tends to be a bit higher, but the effect is relatively small (0.03 for a reduction in salinity from 35 to 32 ppt). Regardless, this effect is wholly unimportant in creating a trend of reduced pH across latitudes, at about constant salinity at a given site.

    I fear I don’t see the connection between what I said (which was that I didn’t know if the Bryne results were valid, but that since they are all we have I accepted them for the sake of argument) and your response. I was not doubting your statements about rainwater. I was saying that Bryne didn’t think the results were from rainwater, and I was accepting their results for the sake of argument.

    Best,

    Chris

    My regards to you as well,

    w.

  141. Wills I really love your ability to look at a set of numbers and then just generate a random anti-AGW conclusion from them. Inspiring stuff.

    “So even without any CO2, if you want to experience “acidification” of the ocean water, just go from Hawaii to Alaska … you didn’t notice the change from the “acidification”? You didn’t have your toenails dissolved by the increased acidity?” is just a glib one liner… do you know many scientists who warn of dissolving toenails – who are you arguing with here?

    “Well, the sea creatures didn’t notice either. They flourish in both the more alkaline Hawaiian waters and the less alkaline Alaskan waters.”… uh huh.

    Surely the logical thing Wilis instead of playing with smoke and mirrors and pwetty gwaphs as you’ve done here, is to actually go though the scientific papers that actually investigate the consequences of ocean acidification, like say http://www.ipsl.jussieu.fr/~jomce/acidification/paper/Orr_OnlineNature04095.pdf

    quite frankly your arguments would only be remotely compelling to an audience that knows very little about the actual science.

  142. Phil. “….the PETM mass extinction involved a jump in CO2 and temperature and an associated extinction of about 95% of marine lifeforms. It took ~80,000 years for the oceanic chemistry to stabilize”

    I presume you are meaning a jump in atmospheric CO2 from ocean degassing as a result of rise in temperature? Are you suggesting that we are headed for a PETM mass extinction with the comparitively miniscule amount of anthropogenic CO2 we are adding to our atmosphere?

  143. maksimovich says:
    June 20, 2010 at 12:11 pm

    Thanks very much for this post, I had not come across the Volk and Hoffert paper about the 3rd pump, which I was unaware of, and which fits the larger picture. This whole discussion was running around in circles over acidity, alkalinity and Ph, by some people who thankfully understood, but also a majority commenting with blissful ignorance. The discussion needed a pointer that acidification of the oceans has far wider and worrying consequences for the oceanic food chain and a larger balance of CO2 remaining in the atmosphere.

  144. I would like to se Willis comment on the results of Hendriks et al. (2010, Estuarine, Coastal and Shelf Science 86:157). This is a massive meta-analysis of 372 studies in which the responses of 44 different marine species to ocean acidification induced by equilibrating seawater with CO2-enriched air had been actually measured. They found that only a minority of studies demonstrated `significant responses to acidification’ and there was no significant mean effect even in these studies. They concluded that the world’s marine biota are `more resistant to ocean acidification than suggested by pessimistic predictions identifying ocean acidification as a major threat to marine biodiversity’ and that ocean acidification `may not be the widespread problem conjured into the 21st century…Biological processes can provide homeostasis against changes in pH in bulk waters of the range predicted during the 21st century.’

    For more on this topic, see:

    http://www.rationaloptimist.com/blog/threat-ocean-acidification-greatly-exaggerated

  145. Phil,

    A change in atmospheric CO2 concentration from 390ppm (current level) to 410ppm will not change pCO2 in the atmosphere in any significant way, so this will not change the CO2 concentrations in ocean water in any significant way.

  146. Richard says:
    June 21, 2010 at 12:53 am

    Phil. “….the PETM mass extinction involved a jump in CO2 and temperature and an associated extinction of about 95% of marine lifeforms. It took ~80,000 years for the oceanic chemistry to stabilize”

    I presume you are meaning a jump in atmospheric CO2 from ocean degassing as a result of rise in temperature? Are you suggesting that we are headed for a PETM mass extinction with the comparitively miniscule amount of anthropogenic CO2 we are adding to our atmosphere?
    ——————-
    280 to 394 ppm in 200 years is minuscule? Not even comparatively.

  147. CO2,

    The human component of CO2 emissions is about 3%. The rest is natural CO2 outgassing.

    Where is your god now?

  148. Phil. says:
    June 19, 2010 at 7:53 pm

    ……But not the same life!
    Case in point, the PETM mass extinction involved a jump in CO2 and temperature and an associated extinction of about 95% of marine lifeforms. It took ~80,000 years for the oceanic chemistry to stabilize.
    _____________________________________________________________________
    Not according to the latest studies
    “….Some scientists have attempted to attribute the timing shift to a drop in CO2 but a new study confirms that carbon dioxide levels were not the cause of the climate shift.” Source

    New Paper in Science by a group lead by Bärbel Hönisch

  149. Mattb says:
    June 21, 2010 at 12:41 am

    quite frankly your arguments would only be remotely compelling to an audience that knows very little about the actual science.

    Bwahahah hahaha this coming from the troll who ADMITS that he doesn’t know enough about the science, admits he doesn’t have the inclination to study it because the IPCC has already done that and he is happy to accept the IPCC conclusions until something better comes along.
    You are a troll Mattb. Your day to day livelyhood depends on the AGW scaremongerring because you are a sustainability manager in your day job.

    To come on to this site and snipe at a man who actually does some work on the subject, whether you agree with his work or not, exposes you to be the despicable low life troll that you are.

    I dare you Mattb, right here and now, publicly, to debate the science instead of sniping like a troll and pointing to links that you probably don’t even understand.
    Whats the matter, sick of being intellectually pummelled by the likes of Richard S Courtney, Eddy Aruda and moi at Jo Novas?

    You’re out of your league here at WUWT Mattb.

  150. Gail Combs says:
    June 21, 2010 at 7:16 am
    Phil. says:
    June 19, 2010 at 7:53 pm

    ……But not the same life!
    Case in point, the PETM mass extinction involved a jump in CO2 and temperature and an associated extinction of about 95% of marine lifeforms. It took ~80,000 years for the oceanic chemistry to stabilize.
    _____________________________________________________________________
    Not according to the latest studies
    “….Some scientists have attempted to attribute the timing shift to a drop in CO2 but a new study confirms that carbon dioxide levels were not the cause of the climate shift.” Source

    New Paper in Science by a group lead by Bärbel Hönisch

    I don’t see the relevance of this paper, it’s referring to a period ~55 million years later!

  151. Pat Moffitt says:
    June 19, 2010 at 8:28 pm

    As someone who has also spent most of his life on, near or in the ocean- my great concern is that ocean acidification will hijack the very real problems we have with our keystone oyster populations. … Despite their keystone status the resources available to address this problem have been paltry at best. (Oysters and disease just don’t make good copy, fund raising or law suits.) Now the oysters will have to find a way to survive the new dictate that all shellfish problems must be caused by CO2.
    ______________________________________________________________________

    I really wish those who are truly concerned with the environment would take a giant step back and look at the whole situation. AGW and various environmental alarms are used to drive hidden agendas that put big bucks into the wealthy’s pockets. This means the REAL problems are starved for funding while the likes of Mike Mann grab the grants and pi$$ the money away on mock science used to generate the required propaganda….

    I will not insult the ladies of the night by likening them to Mr. Mann and company, the ladies at least give value for the dollar spent. Perhaps traitor is the better word since the money is used to damage those it came from.

  152. Gail Combs says:
    June 21, 2010 at 7:16 am

    Hey Gail. I don’t know why you even bothered replying to Phil about the PETM.
    The PETM event is still being hotly debated. No one knows what happened.
    The pointers currently are to volcanic eruptions and/or bollide collisions. CO2 being the cause seems to only come from rabid alarmists like Andrew Glikson.
    Proxy resolutions being in the order of million years +, there is no way they can assign cause to CO2

  153. Richard says:
    June 21, 2010 at 12:53 am
    Phil. “….the PETM mass extinction involved a jump in CO2 and temperature and an associated extinction of about 95% of marine lifeforms. It took ~80,000 years for the oceanic chemistry to stabilize”

    I presume you are meaning a jump in atmospheric CO2 from ocean degassing as a result of rise in temperature? Are you suggesting that we are headed for a PETM mass extinction with the comparitively miniscule amount of anthropogenic CO2 we are adding to our atmosphere?

    Since in order to make this post you must have seen the post I was replying to, why would you make such a stupidly false statement?

  154. Willis, thanks for your feedback re: French article! I was in a bit of a rush, and it was the best I could post without access to my Univ of ILL computer (I have full access to PubMed, etc.)

    The real value of the French paper is not so much their predictions, but discussions of biological plausibility. The problem with CO2 acidification in the ocean is that it occurs at the atmosphere/surface water boundry, where photosynthesis and calcite production are most active. The French point out some interesting findings in regards to observed changes in biota.

    Not sayin’ that this is a reason for cap & trade, I’ve studied the relationship between CO2 and the oceans since, well, 1974, when Collinvaux discussed it in an env. science text! However, to me, this has the gold-standard of biological plausibility = COULD happen under the right conditions of time & concentration.

    I watched the Georges Bank fishery disappear before my eyes in the early 1980′s, and the Atlantic menhaden industry is disappearing as we type….so I get a bit protective of the seven seas! Of the plethora of ills associated with fossil carbon, oceanic acidification is at least plausible. The rest, including runaway Venus effect? Bah!

  155. Phil. says:
    June 19, 2010 at 7:53 pm

    But not the same life!
    Case in point, the PETM mass extinction involved a jump in CO2 and temperature and an associated extinction of about 95% of marine lifeforms. It took ~80,000 years for the oceanic chemistry to stabilize.

    Phil,
    we have so much problem with near-past data and we know so little about, even 1700s and 1800s facts.
    you are willing to take a “glorified speculation about PETM extinction” as absolute truth?

  156. Mattb says:
    June 21, 2010 at 12:41 am
    ….
    Surely the logical thing Wilis … , is to actually go though the scientific papers that actually investigate the consequences of ocean acidification, like say http://www.ipsl.jussieu.fr/~jomce/acidification/paper/Orr_OnlineNature04095.pdf

    Thanks for the reference, Mattb. This looks like an important piece in the acidification argument.

    However, Dana Royer et al, in GSA Today March 2004 (v. 14 no 3, p4ff), and (solo) in Geochimica et Cosmochimica Acta 2006 (v. 70: 5565-75) cite estimates that CO2 concentrations were in excess of 500 ppm and often in excess of 1000 ppm for most of the last 500M years. During much of the Paleozoic, the point estimates (with a huge error band) run about 4000 ppm, while the Mesozoic ran mostly 1000-2000 ppm (with a big error band). The only times it has been comparable to pre-1950 levels have been glacial periods — the Neogene and the late-Carboniferous-Permian glacials.

    What bothers me is that if shell-critters like pteropods can’t survive in such “acidic” environments, how did all the world’s limestone get formed? Was it all during the Carbo-Permian cold spell and the Neogene? Or is it only aragonite shells that are at issue (versus calcite shells)?

    Also, the Orr article you cite provides photos of a pteropod shell suffering shell dissolution in water that was “undersaturated” with respect to aragonite. Was this undersaturation achieved by adding CO2, or by means of a stronger acid like HCl? (Willie Soon claims that such experiments commonly use HCl.) And even though the pteropods studied remained alive, they conclude that they would not expect it to survive under such conditions. This does not seem to follow.

    According to Wiki, pteropods probably evolved during the Paleocene, when CO2 levels were still quite elevated according to Royer’s estimates. How could this have happened?

  157. Baa Humbug: June 21, 2010 at 7:45 am

    Gail Combs: June 21, 2010 at 7:16 am

    Hey Gail. I don’t know why you even bothered replying to Phil…..

    Hey Baa (pardon the informality),

    Every so often you have to give Phil a bit of encouragement to let him know that his stuff is being read. He’s a dedicated little troll, active on every thread, 24/7, so I take him as a litmus test of how badly the warmologists are doing. On most of the other blogs he’d have some chance of success, but unfortunately for him, he’s been assigned to WUWT because it’s the largest threat to the boondoggle, and poor old Phil, even with his faults, is likely the best they’ve got. If he ever stops posting here, I’ll start to worry that they’ve found a new secret weapon. ☺ ☺

    /dr.bill

  158. Phil-
    I’m always amazed when people invoke the Permian extinction—If we could walk the Permian we would need no scientist to tell us the world was turning hostile to life. Remember the Siberian Traps were not just flood basalts but had upwards of 20% pyroclastic flows.

    In a real mass extinction you don’t need statistics or models to know your in trouble.

  159. Mattb says:
    June 21, 2010 at 12:41 am

    Wills I really love your ability to look at a set of numbers and then just generate a random anti-AGW conclusion from them. Inspiring stuff.

    “So even without any CO2, if you want to experience “acidification” of the ocean water, just go from Hawaii to Alaska … you didn’t notice the change from the “acidification”? You didn’t have your toenails dissolved by the increased acidity?” is just a glib one liner… do you know many scientists who warn of dissolving toenails – who are you arguing with here?

    “Well, the sea creatures didn’t notice either. They flourish in both the more alkaline Hawaiian waters and the less alkaline Alaskan waters.”… uh huh.

    Surely the logical thing Wilis instead of playing with smoke and mirrors and pwetty gwaphs as you’ve done here, is to actually go though the scientific papers that actually investigate the consequences of ocean acidification, like say http://www.ipsl.jussieu.fr/~jomce/acidification/paper/Orr_OnlineNature04095.pdf

    quite frankly your arguments would only be remotely compelling to an audience that knows very little about the actual science.

    Well, your post is fascinating, Mattb, but it’s totally content-free. In addition, you recommend a paper that has already been recommended by someone else, and which we’ve already discussed. You really should read the entire thread before commenting if you want to appear as though you are paying attention.

    Come back when you can spell “Willis” (which you managed to mis-spell in two ways) and “pretty graphs”, and bring some science with you, and you’ll be more than welcome. Random nasty sniping as you have done, on the other hand, adds nothing to the discussion and is not welcome in polite society anywhere.

  160. Matt Ridley says:
    June 21, 2010 at 5:18 am

    I would like to se Willis comment on the results of Hendriks et al. (2010, Estuarine, Coastal and Shelf Science 86:157). This is a massive meta-analysis of 372 studies in which the responses of 44 different marine species to ocean acidification induced by equilibrating seawater with CO2-enriched air had been actually measured. They found that only a minority of studies demonstrated `significant responses to acidification’ and there was no significant mean effect even in these studies. They concluded that the world’s marine biota are `more resistant to ocean acidification than suggested by pessimistic predictions identifying ocean acidification as a major threat to marine biodiversity’ and that ocean acidification `may not be the widespread problem conjured into the 21st century…Biological processes can provide homeostasis against changes in pH in bulk waters of the range predicted during the 21st century.’

    For more on this topic, see:

    http://www.rationaloptimist.com/blog/threat-ocean-acidification-greatly-exaggerated

    For those unaware of his work, Matt Ridley is the author of “The Rational Optimist”. He is obviously a man who never noticed that bad news is what sells newspapers …

    Matt, I had not seen the paper you reference. It is a very interesting meta-analysis which backs up my contentions. It says that marine species are much more resilient than people claim, and that most of them don’t even notice the small changes in pH that are predicted (but may not occur) by the end of the century.

    There’s an interesting overview of the paper here, worth reading.

  161. “”” Phil. says:
    June 20, 2010 at 8:26 pm
    John M says:
    June 20, 2010 at 5:59 pm
    Once again, we here the precision of 0.001. And yet…

    “These data were collected before the practice of purifying indicators was adopted, so a correction for mCP impurities was applied to the 2006 pH data: 0.001 units at pH 7.4, increasing to 0.005 at pH 8.1 [Yao et al., 2007]. ”

    So the corrections are greater than the precision?

    That’s frequently the case, that’s why we do calibrations, you do know what precision means don’t you? “”

    I’d lose a lot of hats, if I hung them up on bets as to how accurately somebody can measure something. Even in my career, I seen some bloody clever people come up with interesting ways to measure things much better than historical methods. I recall that early radiocarbon dating methods were of low precision, because people used actual decay observations (of a highly random process) to determine abundances. Then came mass spec methods that let you actually count individual atoms by nuclide species, and the whole game changed.
    When I was at University, doing Physics, we had this one hour lab to use a Fabry Perot 1 cm long Etalon to measure two or three lines in the Neon Spectrum to about 0.1 percent; showing that it was so much more precise than a prism spectrometer.
    So I got interested in the workings of the Fabry Perot device, and did some extra research on the method. About two weeks later, I presented the Professor, with what amounted to a PhD thesis on the Fabry Perot Etalon; along with a listing of about 22 lines in the Neon Red spectrum, which I had accurately measured to one part in 10^7, with their cracker box Etalon.
    Can’t really tell if the Professor appreciated it or not; because he made me spend the next week rewriting the experimental manual on that particular part of the curriculum; to restore that device to its real place in measurment technology.

    I think that Willis has presented so much data on so much variability in every which way of oceanic pH values; that defending a narrow ledge on a hill, on the basis of a bet that one can’t measure (or even resolve) pH to better than 0.01 is one hell of a sorry way to die.

    I expected oceanic pH to be variable; I had no idea that it was all over the map like Willis points out. I’m even surprised to find that electrolytic cell methods can do 0.01; so it is very nice to know that there’s new technology in that area; but I don’t think that Ocean problems are dependent on being able to do that.

  162. CRS, Dr.P.H. says:
    “I watched the Georges Bank fishery disappear before my eyes in the early 1980′s, and the Atlantic menhaden industry is disappearing as we type….so I get a bit protective of the seven seas! Of the plethora of ills associated with fossil carbon, oceanic acidification is at least plausible. The rest, including runaway Venus effect? Bah!”

    The collapse of the George’s Bank was the result of subsidies that created too many boats chasing too little fish. And as the cod populations became smaller and the economics less compelling- more subsidies were added such that we fished them to near exhaustion. Catch quotas were enacted but to make sure that they had no consequences monies were not provided for enforcement. To make sure that under the unlikely scenario that someone might actually get caught- fines were set at a percentage of the days catch. See the NAS study Managing our Marine Fisheries and the shorter Wm Royce lecture on the history of fishery management. spo.nmfs.noaa.gov/mfr504/mfr5047.pdf
    Subsidies are also involved with the menhaden fishery. Remember a crisis was invoked when those Russian trawlers started showing up off our coasts. We declared a 200 mile economic limit and the Feds now had 197 miles of coastline under their control.
    Most people are surprised to learn that prior to our declaration of the 200 mile limit in the 70s there were two relatively small government agencies- The Bureau of Sport Fisheries and the Bureau of Commercial Fisheries. The crisis demanded action and the Nat Mar Fish Serv was formed. NMFS is the old Bur of Commercial Fisheries and the Bur of Sport Fisheries was dissolved. Subsidies started to flow out of Washington to build our own commercial fleet and as a result our fish stocks began to decline. Ted Stevens and cronies got the salmon and Pacific groundstocks, the Bush Family got the menhaden and the Kennedy cronies got the tuna. Currently the commercial fin fishery is allocated 98% of all fin fish (biomass). Sport Fishing is allocated 2% despite generated twice the income, more jobs and actually pays taxes (not being subsidized), pays a wholesale tax on equipment and fuel and 35 million participants. How much subsidy is flowing- well the 1999 Federal Investment Task Force tried to find out but had to concede defeat saying there was so much money flowing through so many agencies with so little paper work that they couldn’t even begin to estimate. (In fairness the real money flows to the large processors not the guys trying to eke out a living)
    The National Academies in a number of studies over more than a decade had enumerated the problems and the solutions. In the recently reauthorized Magnuson Stevens Act- hailed by environmentalists as a great victory— not a single NAS recommendation made it into the bill and several that NAS said were the cause of fishery decline were actually added.
    Most of our serious environmental problems are subsidy driven- from fisheries to agriculture. And the declaration of a crisis is a sign that the government is about to make a problem worse.

    And given the fact that the government failed to address the very real ongoing habitat and disease problems associated with near shore shell fish for 50 years- I’m a bit cynical as to why they are now concerned with what may happen to shellfish in 100 years from CO2

  163. I wanted to return to Chris’s comment, viz:

    We’re on track to have doubled preindustrial CO2 (560 uatm) by around mid-century, which would indeed get you about a 0.25 decrease in surface pH (we’ve already had about 0.1 of that). We are on track to see a >0.4 unit decline in pH by 2100, when atmospheric CO2 will be much higher than 560 uatm (on track for >800 uatm).

    We can fit a polynomial to the changes in CO2 to give us a “business as usual” extrapolation into the future. This assumes both a continued growth and an annually increasing growth in emissions in line with the historically increasing growth in emissions.

    This gives doubled CO2 (560 ppmv), but not by mid-century. It doesn’t occur until 2070. And by 2100, this does not give 800 ppmv as Chris says. Instead, it gives 675 ppmv …

    Using the Bryne observations of .0005 change in pH from a 1 ppmv change in CO2, this indicates that the pH change from now until the year 2100 will not be on the order of 0.4 units as Chris claims. Instead, it will be on the order of 0.14 units

    This is quite near the 0.1 unit pH change that folks claim has occurred since pre-industrial times … I have asked several times for evidence that that change did anything deleterious to the ocean, with no takers.

    We have another estimate of the relationship between pH and CO2 levels, based on the interesting Science Magazine paper cited by Gail Combs above. This gives a relationship of 0.0008 pH units per 1 ppmv change in CO2. This would increase the estimated pH change by 2100 to 0.23 units, which is still very small. We don’t know which figure is nearer the truth. But using either one, we’re not talking about a large change compared to the natural oceanic pH changes that occur daily, monthly, annually, decadally, or on a century long basis.

    It is worth noting, however, that both of those figures are smaller than the canonical figuresfor the change in pH for a given change in CO2, which is 0.0012 units per 1 ppmv. This is more than double the Bryne figure, and 50% higher than the figure from the Science paper cited by Gail.

  164. When baking soda is wet it absorbs (reacts with) atmospheric nitrogen and it becomes urea, (NH2)2CO, that is why it smells like urine…so “rotten” CO2 it’s pee!!
    Our blood is like the sea water, it is buffered,…that is why when you suffer a heart attack doctors give you a baking soda injection. Life is kept by buffering and buffering is an equilibrium of opposing electrical charges (ions)….that is why, also, we living beings have a skin (a holoscience guy would call it a plasma “double layer”) which protect us from any sudden change in the surrounding “environment” but which, unfortunately, does not protect us from a political motivated and funded post normal science which can harm us but more gravely our most sensitive individuals, like our kids. (those pernicious radiations come directly from hell).

  165. Make the following experiment: Open carefully a gas filled water bottle, take it to you mouth (be very, very carefful, I mean that opening below your nose), drink a little…did you feel it sour?….No, you didn’t, didn’t you?..and it was oversaturated with CO2!!
    Now go and find that guy who cheated you, and tell him you won’t believe him anymore!

  166. Pat Moffitt says:
    June 21, 2010 at 11:47 am

    The collapse of the George’s Bank was the result of subsidies that created too many boats chasing too little fish….
    —-
    Thanks, Pat, I know the story all too well. This was stoked by record high prices for atlantic cod & groundfish, and the fisherman got greedy and used smaller & smaller nets, decimating the broodstock. Toss in the Spanish and others, and it was a recipe for disaster. We are watching history repeat itself in Antarctic waters (krill). Dead penguins, anyone?

    The moral of the story is that, although it looks vast, the ocean and its resources can be rather easily pushed to the brink.

    I remember watching Soviet factory ships off of Cape Ann in Mass., processing herring and dumping raw wastewater over the side. Oh well.

    Regarding effects of oceanic acidification, this is something of a biological possibility that I am unwilling to discount without more study. The climate crew are late to adopt this one (ask the folks at Scripps), but now they have embraced it in their slimy grasp, since all of their other death-spiral scenarios have gone awry. Watch for more and more alarmism over this in coming months.

    The real question is, if the oceanic food web is impacted by carbon acidification, what’s to be done about it? The USA and developed nations can’t do much by themselves, as long as China continues their long march towards modernization.

    This represents a very large-scale variation of the old “acid rain” problem that trashed ecosystems like the Finger Lakes region of NY. You can scrub sulfur, but CO2, not so much. Cap & trade won’t solve that one.

    So, as “global warming” sets into the sunset due to the ongoing Grand Solar Minimum and the distortions of the climatologists & advocates, watch for more & more alarmism/panic over oceanic acidification.

    I just laugh! The solution won’t be easy, but there are some good alternatives being kicked around. Just get the damn atmospheric people out of the way.

  167. Enneagram says:
    June 21, 2010 at 12:30 pm
    When baking soda is wet it absorbs (reacts with) atmospheric nitrogen and it becomes urea, (NH2)2CO, that is why it smells like urine…so “rotten” CO2 it’s pee!!

    In your dreams! Go away and learn some chemistry.

  168. CRS, Dr.P.H. says:
    June 21, 2010 at 1:10 pm “Regarding effects of oceanic acidification, this is something of a biological possibility that I am unwilling to discount without more study.”

    I don’t have a problem with studying this but as the FOARAM Act shows- that is not we are going to do. Foaram funding assumes the deleterious effect of ocean acidification- and provides grants to demonstrate the deleterious effects. When funding limits the answers we can learn nothing.

  169. Phil. says:
    June 20, 2010 at 8:26 pm

    “you do know what precision is, don’t you?”

    Certainly. But if my financial guy came to me telling me my net worth to +/-$0.01, but with an “adjustment” from 5 years ago of -$26,237.56, I don’t know about you, but I’d be asking questions.

    But more to the point, the stated precision requires taking into account both the precision of the today’s measurements and the precision of the correction made for the impure indicator compound used in the past. I guess that assumes that the level of impurity was always the same. You’re not a synthetic chemist I take it.

    But if you want to talk accuracy instead of precision, back to my reference from 2004:

    Combining the last three random uncertainties
    (by the square root of the sum of squares of each accuracy)
    leads to a true accuracy in our pH determination of
    ±0.004 pH units plus a possible systematic error of ±0.004 pH
    from the introduction of the hydrogen ion seawater scales.

    However the
    magnitude of the averaged difference between measured and
    calculated pH from the 112 hydro cast samples and 34 surface
    samples are –0.010 and –0.034, respectively. This therefore
    exceeds our estimate of the precision and accuracy of our pH
    measurement by a lot. The difference may result from errors in
    our pH measurement, from errors in the TCO2 or TA measurements,
    or alternatively and more likely, the constants used to
    calculate pH from TA and TCO2, or all three. The pH error arising
    from our TCO2 and TA accuracy is of the order ±0.005
    units. Therefore errors in the constants seem the most probable
    cause.

    I’m asking what I think is a reasonable question. The recent paper we are discussing has few experimental details on errors and uncertainty. They cite references from the late 80s/early 90s as their basic technique. I am citing a paper from 2004 that shows greater levels of uncertainty for the technique.

    Can you provide me with the level of detail needed to show current levels of precision and accuracy are higher than stated in the 2004 paper?

    George E. Smith

    “…defending a narrow ledge on a hill, on the basis of a bet that one can’t measure (or even resolve) pH to better than 0.01 is one hell of a sorry way to die.”

    Probably wise council, but that would take all the fun out of it.

    The technique we’re debating does not use an electrolytic cell, but is a spectrophotometric technique based on spectral changes in a pH-sensitive organic probe molecule. I’m interested in the pH techniques as a chemist, and also because I think it fits with the general tendency of researchers in “hot” areas (not just climate science) to overhype their results and the certainty of their results (at least in the PR releases they seem to be addicted to).

    It is amazing work, but like everything else, can be oversold And like it or not, ocean pH is becoming the new poster child for the “we need to do something” advocates.

  170. Sorry WILLIS – “running too fast” is how you excuse your sloppy typing maybe you could afford the same latitude to us mere mortal posters. Very Moncktonesque of you to dismiss me with patronising smugness rather than address the issues.

  171. Pat Moffitt says:
    June 21, 2010 at 3:40 pm
    CRS, Dr.P.H. says:
    June 21, 2010 at 1:10 pm “Regarding effects of oceanic acidification, this is something of a biological possibility that I am unwilling to discount without more study.”

    I don’t have a problem with studying this but as the FOARAM Act shows- that is not we are going to do. Foaram funding assumes the deleterious effect of ocean acidification- and provides grants to demonstrate the deleterious effects. When funding limits the answers we can learn nothing.
    ———–
    REPLY: Thanks, Pat, you know yer stuff! Here’s a link for everyone:

    http://www.us-ocb.org/documents/2008-2009_OCB_OA_highlights.pdf

    We OBJECTIVE scientists have an opportunity to get something right in terms of the study of atmospheric carbon deposition! I look forward to seeing some real science being performed for once!

    Instead of the legacy of spooky old James Hansen, trying to frighten children with his nightmare-inducing scare-stories about Earth de-evolving into another Venus, we have a great opportunity to accurately measure biota, ocean alkalinity, and ascertain mitigation/remediation steps if needed. Scripps are way ahead on this one.

    I’m actively involved in this work with University of Illinois in Urbana and will keep you posted on developments. No matter what we find, it only matters if China and India come onboard. We think they will.

  172. CRS, Dr.P.H. –A request in this new era of ocean acidification- put in a good word whenever possible for oyster rehab (Dermo, MSX and habitat loss) I have seen too many critical environmental issues hijacked in my career. And lets spend most of the early monies on formulating what data is needed and its collection before we jump to the answer . You mention Scripps- the home of one of my heroes- John Isaacs- a man who many years ago took the time to talk some sense into a very young man just starting out in the field.

  173. Pat Moffitt says:
    June 21, 2010 at 8:19 pm
    CRS, Dr.P.H. –A request in this new era of ocean acidification- put in a good word whenever possible for oyster rehab (Dermo, MSX and habitat loss) I have seen too many critical environmental issues hijacked in my career. And lets spend most of the early monies on formulating what data is needed and its collection before we jump to the answer . You mention Scripps- the home of one of my heroes- John Isaacs- a man who many years ago took the time to talk some sense into a very young man just starting out in the field.

    You’ve got a deal! I’ll be back to WUWT sometime when we are closer to publication. VERY interesting stuff going on at my alma mater in Urbana!

  174. Mattb says:
    June 21, 2010 at 6:45 pm

    Sorry WILLIS – “running too fast” is how you excuse your sloppy typing maybe you could afford the same latitude to us mere mortal posters. Very Moncktonesque of you to dismiss me with patronising smugness rather than address the issues.

    Mattb, I did a quick mental subtraction of 8.05 minus 7.65 and got 0.5 … so sue me. Unless you can assure us that you have never made a mathematical error because you were moving too fast, to call that “Monctonesque” and abuse me for a simple subtraction mistake is arrogant, unpleasant, and puerile.

    It is, however, typical of people who have nothing of substance to say. Hey, I made a math error. Unlike a mainstream climate scientist like Michael Mann (see the half-dozen posts on the Tiljander fiasco) I admitted to my error. It makes no difference to the substance of my claims. Get over it. You want to get on someone’s case for an error? Go bother Michael.

  175. Pat Moffitt says:
    June 21, 2010 at 8:19 pm

    CRS, Dr.P.H. –A request in this new era of ocean acidification- put in a good word whenever possible for oyster rehab (Dermo, MSX and habitat loss) I have seen too many critical environmental issues hijacked in my career.

    This to me is one of the biggest tragedies of the onslaught of global warming alarmism. Global warming has stolen all of the spotlight away from what are very real environmental issues.

    In Fiji, a friend and I were concerned about the foreign longline fishermen raping the Fijian waters. He went to talk to the local Greenpeace folks to see if he could enlist their assistance, only to be told that they couldn’t assist the fish … because they were putting all of their energy into fighting climate change.

    So yes, indeed, put in a good word for the oysters and all of the other real issues that the watermelon greens have forgotten about in their drive to halt all progress and turn back the clock.

  176. Sorry Willis – I missed an i in your name – sue me. I don’t give a rats about your maths mistake, and all I did was highlight your own arrogant, unpleasant and purile response to me. On one hand you make out me missing an “i”is somehow worthy of comment, an other other hand I’m arrogant and purile for asking for the same leeway you afford yourself. Note – of course I think your 0.5 is of zero consequence, but so was my Wills.

    earth to Eschenbach… am I getting through?

  177. Mattb, you came in here and started mouthing off with your very first sentence by saying:

    Wills I really love your ability to look at a set of numbers and then just generate a random anti-AGW conclusion from them. Inspiring stuff.

    You went on to accuse me, without a scrap of scientific argument or a single citation, with “playing with smoke and mirrors and pwetty gwaphs”, as though there were something wrong with my graphs because they are interesting to look at … do you think your cheap innuendo actually fools or convinces anyone? My graphs stand or fall on the numbers they portray, and you can’t find anything wrong with the numbers so you attack how they look???

    You then invited me “to actually go though the scientific papers that actually investigate the consequences of ocean acidification, like say http://www.ipsl.jussieu.fr/~jomce/acidification/paper/Orr_OnlineNature04095.pdf

    without noticing that I had already done exactly that.

    You closed by saying that “quite frankly your arguments would only be remotely compelling to an audience that knows very little about the actual science”, as though you had provided some actual science in your post, or would recognize it if you saw it.

    Now you want to highlight my “arrogant” response? BWA-HA-HA-HA … My friend, you came in here with nothing but snide remarks and personal attacks and enough attitude to sink a large ship. You don’t have the standing to say a single word about my or anyone else’s attitude. You got your nastiness thrown back in your face, and now you want to complain? I don’t apologize for doing that. That’s what happens when you walk in the door with personal attacks instead of science, you get the same treatment as when a puppy messes on the floor – you get your nose rubbed in it.

    If you want to discuss the science, fine. If you think that there are material errors in my work, you are welcome to point them out. If you have scientific papers that support your claim, please cite them, I’m here and more than happy to discuss any scientific issues you care to raise.

    But starting out with personal attacks, innuendo, and general unpleasantness? Sorry, that’s poor tactics that will get you bounced out of polite conversations anywhere on the planet. You should try posting under your own name so that you have to stand behind your words, you might actually get some traction. At present, all you are doing is giving a bad name to decent people who honestly believe in the AGW hypothesis and are willing to have a scientific discussion and debate about the issues …

  178. CO2 says:
    June 20, 2010 at 9:10 am

    tallbloke says:
    June 20, 2010 at 5:01 am
    “2) (And you didn’t try to address this one, presumably because you know you’ve been caught with your pants round your ankles) Co2 dissolved in water forms an acid. Yet you state that “A warmer ocean holds less CO2. Ocean’s with less CO2 become more acidic”.

    I should have added, “Because of other factors”, a warmer ocean…
    Ocean acidity is not only a simple function of CO2 disolving in water, it involves the bio-mass from Phyto-plankton and Zooplankton down, which sequester CO2 drawing on the disolved CO2 carrying it to both the deep waters and the ocean floor. This is referred to as the solubility pump and the biological pump. This bio-mass of Phytoplankton and Zooplankton, residing close to the surface, is threatened by the warming of colder oceans, resulting in less absorbtion of CO2, increasing the disolved CO2 level, hence acidity. The whole issue is far more complex than a discussion about Ph, acidity and alkaline. While a warmer ocean may absorb less CO2, the CO2 level will still increase if the rate of sequestration drops disproportionally.

    Oh dear. Trying to hide your error with extra complication and further errors doesn’t change the incorrectness of your original statement. How is the warming of oceans going to increase the disolved(sic) co2 level, CO2?

    tallbloke says:
    June 20, 2010 at 5:01 am
    1) if the ocean is not acidic to begin with (it isn’t) , then it can’t become “more acidic”, only less alkaline. It can undergo a process of acidification however, as Chris said.

    what’s the difference between ‘a process of acidification’ and more acid?

    One is correct the other (yours) is wrong.

    As for the pants, they don’t need ironing yet.

    Correct, they need washing first.

  179. Okay. So mankind puts a little dab of CO2 into the atmosphere that was never intended by Nature. But, plants gobble up CO2. So, plant life expands commensurately by absorbing our little dab extra of CO2. And so, all is good. I am not any kind of scientist, but that line of thought makes a lot of sense to me. Does science not back up that simple line of reasoning?

  180. Smokey says:
    June 21, 2010 at 7:05 am

    CO2,

    The human component of CO2 emissions is about 3%. The rest is natural CO2 outgassing.

    Where is your god now?
    ————————-
    Natural CO2 outgassing, what do you mean by natural? It depends on water temperature and since the oceans are warming and outgassing more CO2, is that still natural? I presume that by natural you mean that it is the oceans doing it of their own accord. However, if the warming of the oceans is caused by an unnatural phenomenon like humans, doesn’t that change the meaning of natural?

    Over the past 10,000 years the atmospheric CO2 level has fluctuated no more than 10-15 ppm around an equilibrium of 280ppm. We are now at 394ppm, a rise of 114ppm over just 200 years.

    Quote; “A massive store of excess carbon inaccessible to the carbon cycle for many 10′s of millions of years is being rapidly reintroduced into the system in an extraordinarily short time period. Not surprisingly the atmospheric CO2 concentration is rising very rapidly indeed. The atmospheric CO2 concentration is out of equilibrium (there’s a large nett flux into the atmosphere from previously long-sequestered sources), and the atmospheric CO2 concentration is being driven up towards some new equilibrium concentration.”

    My God? That would have to be Neptune.

  181. Smokey says:
    June 21, 2010 at 7:05 am

    Where did that 3% figure come from and on the basis of what?
    As for Neptunes location? Have a guess and belatedly, he’s taken to antacid tablets.

  182. CO2,

    All CO2 is natural. By convention I’m using ‘natural’ to differentiate non-human emitted CO2. But you knew that.

    CO2 has been much higher in the geologic past, and life flourished to a greater extent when CO2 levels were much higher. It is simple cherry-picking to select an arbitrary time span like 10,000 years.

    As you can see here, the human component of CO2 is ridiculously small. That is where the ≈3% figure came from. And since plants respond to more available fertilizer, any excess will eventually be consumed over time.

    Further, there is nothing to worry about because we’re talking about the tiny human addition to a tiny trace gas. Water vapor has about 1,000 times the effect of CO2 as a so-called greenhouse gas. But it is much more difficult to tax water vapor.

    Since a rise in CO2 always follows a rise in temperature, at all time scales, the current rise in CO2 must be due to prior temperature increases, and not vice-versa. CO2 does not cause measurable warming; warming causes more CO2.

    Since CO2 is a function of temperature, it is clear that the current rise in CO2 is due primarily to ocean outgassing. If CO2 caused warmer temperatures, then there would be much greater correlation.

    To summarize: CO2 is entirely beneficial. It does not cause any but the most minor, insignificant warming, which is too small to measure; otherwise, the climate sensitivity number would be agreed by everyone. The current rise in CO2 is primarily the result of the rise in temperature since the LIA, and is only coincidental with the industrial revolution.

    Rising CO2 can not cause runaway global warming. The incessant drumbeat of “carbon” is based on the big lie, repeated until the scientifically illiterate general public gradually accepts the premise that something “must be done.”

    That ‘something’ is to sharply raise taxes, by adding a hidden “carbon” tax to all goods and services across the board. It is an insidious and regressive tax that will hit the poor the hardest, and it will certainly cause starvation among the world’s one billion people who live on less than one dollar a day.

    But the government propagandists pushing the CO2=CAGW lie simply do not care about the resulting starvation. To them, causing death by demonizing and taxing a harmless and beneficial trace gas is a small price to pay for money, power and control. That is the real problem.

  183. tallbloke says:
    June 20, 2010 at 5:01 am
    1) if the ocean is not acidic to begin with (it isn’t) , then it can’t become “more acidic”, only less alkaline. It can undergo a process of acidification however, as Chris said.

    what’s the difference between ‘a process of acidification’ and more acid?

    One is correct the other (yours) is wrong.
    ————————————-
    Oh dear, they mean the same so how can one be wrong?
    ————————————-
    Oh dear. Trying to hide your error with extra complication and further errors doesn’t change the incorrectness of your original statement. How is the warming of oceans going to increase the disolved(sic) co2 level, CO2?
    ————————————–
    Because it is only an initiation of the process over a relatively short period. CO2 disolves into the ocean (solubility pump) and the biomass (biological pump) sequesters CO2. Phytoplankton act in two ways; they fix CO2 as organic carbon during photosynthesis and form shells from calcium carbonate. Marine snow carries both of these forms of carbon away from the atmosphere and surface waters to reservoirs in the deep oceans and ocean sediments.
    Warming of the ocean causes stratification which inhibits upwelling of the particles, necessary for the plankton to feed on. When this happens the declining phytoplankton will sequester less Co2; if they simply become extinct, no CO2 at all. The moment this sequestration falls below the balance point which has existed for the present interglacial has severe consequences. Given that the rate of atmospheric CO2 increase is going up rapidly and the rate of phytoplankton sequestration will decline, more and more CO2 will remain in the ocean, increasing the acidity. A total loss of phytoplankton will disrupt the entire oceanic food chain.
    This is the process of acidification, more acid if you like.

  184. Excellent post Smokey. I understand that it was directed at another, but it effectively answers my question too.

  185. CO2 says:
    June 22, 2010 at 5:56 am

    what’s the difference between ‘a process of acidification’ and more acid?

    One is correct the other (yours) is wrong.
    ————————————-
    Oh dear, they mean the same so how can one be wrong?

    No they don’t mean the same. If the alkaline ocean undergoes acidification it will become less alkaline, until it gets below 7ph at which point it becomes acidic. If it drops further below 7 in ph value, then and only then can you correctly say “The ocean is becoming more acidic.”

    I’ve done with this. If you still don’t get it, tough cookies, stop blabbing on at me about it.

    Phytoplankton act in two ways; they fix CO2 as organic carbon during photosynthesis and form shells from calcium carbonate. Marine snow carries both of these forms of carbon away from the atmosphere and surface waters to reservoirs in the deep oceans and ocean sediments.

    And this makes the ocean “more acidic” how? Sedimented carbonates are pretty chemically stable are they not?

  186. John M says:
    June 21, 2010 at 6:23 pm
    Phil. says:
    June 20, 2010 at 8:26 pm

    “you do know what precision is, don’t you?”

    Certainly. But if my financial guy came to me telling me my net worth to +/-$0.01, but with an “adjustment” from 5 years ago of -$26,237.56, I don’t know about you, but I’d be asking questions.

    Quite possibly but it’s hardly comparable, a better analogy would be to make a measurement of a 10.00V source and get a result of 10.03 with a precision of ±0.01.

    But more to the point, the stated precision requires taking into account both the precision of the today’s measurements and the precision of the correction made for the impure indicator compound used in the past. I guess that assumes that the level of impurity was always the same. You’re not a synthetic chemist I take it.

    Which would have no effect on the precision! Also no reason to suppose that it was a different batch of indicator.

    I’m asking what I think is a reasonable question. The recent paper we are discussing has few experimental details on errors and uncertainty. They cite references from the late 80s/early 90s as their basic technique. I am citing a paper from 2004 that shows greater levels of uncertainty for the technique.

    Your paper from 2004 quotes the same references from “the late 80s/early 90s” and describes a modification to the technique to use a CCD detector (a cheaper, quicker method) rather than use a scanning spectrophotometer. The paper shows that they were able to get similar precision (long term ±0.0032, short term ±0.0012) with their modification of the technique.
    Your inherent supposition appears to be that ‘newer = more precise’, whereas it’s clear that the authors of the 2004 paper were prepared to sacrifice some precision for a cheaper, quicker variation of the technique.

  187. re Smokey: June 22, 2010 at 5:56 am

    That ‘something’ is to sharply raise taxes, by adding a hidden “carbon” tax to all goods and services across the board. It is an insidious and regressive tax that will hit the poor the hardest, and it will certainly cause starvation among the world’s one billion people who live on less than one dollar a day.

    But the government propagandists pushing the CO2=CAGW lie simply do not care about the resulting starvation. To them, causing death by demonizing and taxing a harmless and beneficial trace gas is a small price to pay for money, power and control. That is the real problem.

    I would (sadly) add the following to your commentary:

    Given the many individuals who have been, and still are, involved in various hot/cold/other scares going back to the 70′s or earlier, and who have been active in the “eugenics/over-population” issue, the starvation is hardly an accidental byproduct of the alarmism. For many of them, it is the ultimate purpose.

    /dr.bill

  188. Willis Eschenbach says:
    June 22, 2010 at 12:31 am
    “This to me is one of the biggest tragedies of the onslaught of global warming alarmism. Global warming has stolen all of the spotlight away from what are very real environmental issues.”

    They do more damage than simply stealing the spotlight -they make impossible demands that force all resource problems and remediation to fit their ideological paradigm. Pac. Salmon problems as an example must always have dams as the cause. Yet the most stressed salmon stocks are Oregon coastal coho which have neither dam nor habitat issues. (The problem is the phase of the PDO, mixed stock harvest and the cascade effect from not allowing sufficient escapement – marine derived nutrients- to enter the freshwater system.) For the Atlantics its a decline in pH which disrupts smoltification caused by the decline in agriculture, regrowth in forest and disruption in fire cycle. Again the greens champion dam removal- even though there are no salmon in rivers without dams. And actively oppose a liming project to remedy this problem.
    They don’t just steal the spotlight- they sacrifice the environment on the altar of their ideology.

    Keep up the good fight.
    Pat

  189. Smokey says:
    June 22, 2010 at 5:56 am
    CO2,
    All CO2 is natural. By convention I’m using ‘natural’ to differentiate non-human emitted CO2. But you knew that.
    ————————
    By what convention? I wasn’t talking about the CO2 molecule. So what’s the point, if all CO2 is natural, what’s your differentiation about?
    ————————
    CO2 has been much higher in the geologic past, and life flourished to a greater extent when CO2 levels were much higher. It is simple cherry-picking to select an arbitrary time span like 10,000 years.
    —————————
    The time span is not arbitrary, it refers to an interglacial period. Okay, so I will give you 20 million years and cite you a figure of 280ppm for interglacials and 170ppm for glacials.
    ————————–
    As you can see here, the human component of CO2 is ridiculously small. That is where the ≈3% figure came from. And since plants respond to more available fertilizer, any excess will eventually be consumed over time.
    ————————-
    Your link provides information about the sources of CO2 , NOT the percentage of CO2 in the atmosphere. It shows an increase of 11.7 Gtonnes of CO2 per year in the 1990’s.
    ————————–
    Further, there is nothing to worry about because we’re talking about the tiny human addition to a tiny trace gas. Water vapor has about 1,000 times the effect of CO2 as a so-called greenhouse gas. But it is much more difficult to tax water vapor.
    ————————–
    A stupid argument, science is well aware of the fact that water vapour has the largest warming effect. However, water vapour is not a gas, it is suspended H2O and has a cycle of hours or days. If the original “tiny trace of gas” of 280ppm has kept the earth’s temperature to what we have had since 200 years ago, and a reduction to 180ppm causes a glacial period, then an increase of 114ppm is leading us into uncharted territory.
    —————————-
    Since a rise in CO2 always follows a rise in temperature, at all time scales, the current rise in CO2 must be due to prior temperature increases, and not vice-versa. CO2 does not cause measurable warming; warming causes more CO2.
    ————————-
    Okay, keep repeating this fallacy, and some will believe it I guess.
    ————————–
    Since CO2 is a function of temperature, it is clear that the current rise in CO2 is due primarily to ocean outgassing. If CO2 caused warmer temperatures, then there would be much greater correlation.
    ————————–
    Since the premise is false, the conclusion is too. The graph you link to doesn’t tell me anything. Point me to reputable science that claims that CO2 always follows temperature rise. It is possible under certain circumstances, but presently the opposite is beyond dispute. Please don’t say that short term there is cooling while CO2 is rising and that this proves that CO2 follows temperature. Do some more reading beyond the simplistic.
    ————————–
    To summarize: CO2 is entirely beneficial. It does not cause any but the most minor, insignificant warming, which is too small to measure; otherwise, the climate sensitivity number would be agreed by everyone. The current rise in CO2 is primarily the result of the rise in temperature since the LIA, and is only coincidental with the industrial revolution.
    ————————-
    Cause and effect, so what caused the rise in temperature?
    ————————
    Rising CO2 can not cause runaway global warming. The incessant drumbeat of “carbon” is based on the big lie, repeated until the scientifically illiterate general public gradually accepts the premise that something “must be done.”
    —————————-
    Can you quote the science rather than the rhetoric?
    ————————
    That ‘something’ is to sharply raise taxes, by adding a hidden “carbon” tax to all goods and services across the board. It is an insidious and regressive tax that will hit the poor the hardest, and it will certainly cause starvation among the world’s one billion people who live on less than one dollar a day.
    —————————–
    Hello, Lord Christopher Monckton.
    —————————-
    But the government propagandists pushing the CO2=CAGW lie simply do not care about the resulting starvation. To them, causing death by demonizing and taxing a harmless and beneficial trace gas is a small price to pay for money, power and control. That is the real problem.
    ————————-
    Indeed, such nasty creatures these propagandists, determined to kill innocent people. Demonising CO2 the beneficial plant food, this harmless gas of which we should have as much as possible. Apologies for the sarcasm.

  190. dr.bill says:
    June 22, 2010 at 8:24 am

    “….the starvation is hardly an accidental byproduct of the alarmism. For many of them, it is the ultimate purpose.”

    Demeaningly cynical.

  191. CO2,

    You may think that nitpicking everything said shows that you are intelligent and up to speed on the subject, but all it shows is insecurity covered up by ad hominem attacks [Monckton, etc].

    Arbitrarily changing your original 10,000 year assertion to 20 million years is still cherry-picking. Using the time scale of the biosphere’s use of CO2 does away with the cherry-picking. I can provide you with charts similar to the one I provided up-thread, going back 4.6 billion years if it helps. They show that CO2 has been almost twenty times higher than today, in both hothouse and icehouse epochs, and during times when life thrived in much higher CO2 concentrations — without any runaway global warming.

    I stand by every statement I made, and while you demand citations [which I routinely gave], you provided none yourself, but only off the cuff opinions based on your scientific flawed assumptions.

    For one example of many, you stated that: “…water vapour is not a gas, it is suspended H2O and has a cycle of hours or days.”

    In fact, water vapor is a gas. Since your level of understanding is so rudimentary and filled with misconceptions, I suggest you read the WUWT archives from the beginning, so you can have an intelligent conversation without making such basic scientific errors.

  192. Oh dear, 200+ posts and no one commented on the title? Love the reference to “The Electric Kool-Aid Acid Test”–haven’t thought of it in a long while, but it’s one of my favorite books. Thanks again, Willis.

  193. CO2 says:
    June 22, 2010 at 9:38 am

    Paul Erlich wants a much much lower human population. Given that Gordon Brown and other leaders said there was only months left until we reached the famous tipping point, and that they obvously wants to reduce the population of the world to avoid it, I would very much like to see how they would reduce it?

    Mass murder? Mass starvation? Mass sterilisation? What society do they want? How will they achieve it?

    My suspicion is that they like Pol Pots solution.

    I hope you dont wear glases, CO2. I hope you dont know any foreign language.
    Dont raise your hand in class.

  194. Bill S says:
    June 22, 2010 at 11:23 am

    “Oh dear, 200+ posts and no one commented on the title? Love the reference to “The Electric Kool-Aid Acid Test”–haven’t thought of it in a long while, but it’s one of my favorite books. Thanks again, Willis”

    And with the new PNAS “blacklist” paper it sure seems clear now “that either your on the bus or off the bus.”

  195. This means that for the top 800 metres of the ocean, where the majority of the oceanic life exists, the human induced change in pH was -0.013 over 15 years. This was also about the amount of pH change in the waters around Hawaii.

    Now, remember that the difference in pH between the surface water in Hawaii and Alaskan is 0.50 pH units. That means that at the current rate of change, the surface water in Hawaii will be as alkaline as the current Alaskan surface water in … well … um … lessee, divide by eleventeen, carry the quadratic resdual … I get a figure of 566 years.

    You didn’t just divide one into the other did you? It’s a log scale, and that just doesn’t work that well.

    Besides when dividing one into the other I get 577.

  196. Caleb says:
    June 20, 2010 at 2:07 am

    Ed,

    I can’t supply a link, but I recall reading about scientists studying the life thriving around a deep-sea vent. While studying some giant clams they noted a strange liquid oozing front a crack near the vent. Upon investigation, it turned out to be CO2, which is liquid under the extreme pressures of deep sea environments (as it is under the pressure inside a CO2 fire extinguisher.)

    Apparently the liquid CO2 did not form puddles on the sea bottom, but rapidly dissolved into the water. It had no apparent effect on the nearby deep-sea vent life forms. I have no idea what the Ph of the water was.

    Does anyone know more about this subject?

    Sounds like the CO2 was under sufficient temperature and pressure to become a supercritical fluid http://en.wikipedia.org/wiki/Supercritical_fluid – which are noted for being excellent solvents and are used industrially as such.

  197. CO2 says:
    June 22, 2010 at 9:38 am

    dr.bill says:
    June 22, 2010 at 8:24 am

    “….the starvation is hardly an accidental byproduct of the alarmism. For many of them, it is the ultimate purpose.”

    Demeaningly cynical.

    Unfortunately in this world, cynicism on the megaton scale does not stop you from being right.

  198. Z says:
    June 22, 2010 at 1:35 pm
    Sounds like the CO2 was under sufficient temperature and pressure to become a supercritical fluid http://en.wikipedia.org/wiki/Supercritical_fluid – which are noted for being excellent solvents and are used industrially as such.

    Pressure obviously supercritical, the temperature of the CO2 would have to be over 31ºC to be a supercritical fluid.

  199. CO2: June 22, 2010 at 9:38 am

    dr.bill: June 22, 2010 at 8:24 am
    “….the starvation is hardly an accidental byproduct of the alarmism. For many of them, it is the ultimate purpose.”

    Demeaningly cynical.

    You may think so, CO2, but I am not at all cynical. I am simply saddened by the inhumanity of some of my con-specifics. You need go no further than to read the publications of the Club of Rome and its members and hangers-on in order to see the reality of this. For example:

    From “The First Global Revolution”: “The common enemy of humanity is man. In searching for a new enemy to unite us, we came up with the idea that pollution, the threat of global warming, water shortages, famine and the like would fit the bill. All these dangers are caused by human intervention, and it is only through changed attitudes and behavior that they can be overcome. The real enemy then, is humanity itself.”

    Henry Kissinger: “Control oil and you control nations; control food and you control the people; control money and you control the world.”

    For reasons that baffle me, they have publicly produced many such plans and pronouncements over the years, but few people remember them, or perhaps they don’t want to believe that people could have such base motivations.

    Here’s a list of verbatim quotes that was posted by commenter Jason on WUWT about a month ago: “In Their Own Words”. Make yourself aware of reality, and perhaps get your social standing checked out, or even have a DNA profile done. You might not be on the ‘good list’.

    /dr.bill

  200. Since you’re citing and interpreting Monterey Bay Aquarium data, I contacted one of our water quality researchers. Here’s what they have to say:

    If you add a basic trendline to the data set, it actually shows that there is a longterm decrease in the pH of our intake water. The slope of the line is −4.1283e−006. They can use the data, but it actually does more to reinforce ocean acidification using it at face value.

    Ken Peterson, Communications Director, Monterey Bay Aquarium

  201. The authors of this paper are definitely overstating the certainty of their data. The spectrophotometric procedure may have an internal precision of around 0.001 absorption units, but the total reportable uncertainty must be determined by propagation of the error throughout all calculations performed. Their calculations rely on the relative amounts of the two ionization states of m-cresol purple. These ionization states are related to the dissociation constant associated with loss of a proton from the phenolic group. Ultimately, this pKa value will have been determined using a method that measures the concentrations of the acidic and basic species as a function of pH. The accepted pKa (from the Handbook of Acid-Base Indicators) for the HL = H + L equilibrium of m-cresol purple is 8.32 (indicating an uncertainty of no less than ±0.01). The spectrophotometric method for measurement of the pH of a solution containing m-cresol purple must have been determined from the rearrangement of the equilibrium constant relation K = H*A/HA combined with the mass balance equation HA(total) = HA + A. Thus, propagation of the error in the calculated pH value cannot be less than the uncertainty of the measured pKa used in the calculation.

    I took a look at the references to the author’s method to better understand the basis of their claims. The article referenced an earlier paper that claims the spectrophotometric method is precise to within ±0.005 pH units. The derived equation utilizes a calculated pKa value from an equation expressing the pKa as a function of both the ionic strength and temperature. This equation provides an accurate description of the behavior of the pKa against these external influences. However, the authors use the calculated pKa value without noting its uncertainty, which implies that they consider it to be considerably less than the error in the absorbance readings. This is simply not possible; no reported pKa value has ever been determined with an uncertainty less than ±0.001. Furthermore, nearly all of the highest quality pKa values, measured at a single temperature and ionic strength condition and determined using acceptable methodologies, have reported errors of ±0.01 to ±0.05.

    The experimental pKa determinations of m-cresol purple must have been made against a calibrated pH meter using a technique relating species concentration to proton activity as described by Albert and Serjeant (1984). The precision of the primary pH standards (traceable calibration buffer solutions adhering to IUPAC standards) have uncertainties of ±0.01 pH units (2-sigma). Therefore, in accordance with IUPAC specifications, a properly calibrated pH meter has a minimum uncertainty of ±0.01 to ±0.03 pH units. Hence, each pKa value obtained and subsequently used in the multiple regression equation, pKa = f(T, I), will have an uncertainty of at least ±0.01 to 0.03. The calculated best-fit coefficients will have additional standard errors from the regression. Hence, the pKa value used in the pH determination cannot have an uncertainty small enough to ignore it in the final reported pH uncertainty.

    It is obvious that the spectrophotometric pH measurement technique is no more certain than any other accepted pH measurement technique used by chemists worldwide. A reasonable lower bound for the pH error of seawater is ±0.01 – 0.05 (approximately two to ten times greater than the author’s claimed max error). A reasonable upper bound for the error associated with a high-precision pH measurement of seawater by this technique, considering the likely magnitude of the errors associated with temperature, ionic strength, spectral purity and total concentration of the dye, is probably around ±0.10. As others have pointed out, the true uncertainty in the pH measurement far exceeds any changes associated with observed pH values of seawater. The peer-review process of this paper has completely failed to ensure that these authors critically evaluate the uncertainty of their measurements.

  202. dr.bill says:
    June 22, 2010 at 2:25 pm

    I had a commenter at http://www.scientificamerican.com/article.cfm?id=experts-warn-climate-change-disrupts-agriculture tell me this about my comment lauding Norman Borlaug for feeding a starving world.
    “Borlaug did more to increase the human population than whatever, and in so doing, he increased the suffering. If the gains in production had gone to increasing wealth and the education of girls so as to not increase population, you would have a point, but they didn’t. Borlaug just made the ultimate catastrophe worse.”

    So Borlaug by feeding a starving people made the problem worse. You see Ehrlich and Holdren weren’t wrong— Borlaug just prolonged the suffering. Perhaps that is why Borlaug passed recently with little note and Holdren is our Science adviser.

    It seems that some are so angry that the apocalypse didn’t happen that they are now trying to create it.

    There is a word for this – misanthropy.

  203. Phil. says:
    June 22, 2010 at 8:07 am

    “Also no reason to suppose that it was a different batch of indicator.”

    What a wonderfully faith-based asumption. So the same batch of indicator was used in 1991 as in 2006?

    If a correction was applied, isn’t the total precision uncertainty the uncertainty of the measurement itself plus the uncertainty of the correction (part of the propagation of error issue mentioned by ZP)?

    Anyway, here’s the abstract for Yao 2007, which is the reference for making the correction.

    Abstract: Spectrophotometric pH measurements have been widely used in oceanic CO2?system research. However, impurities in indicator dyes from different manufacturers may cause uncertainty in measured pH values. In this work we report initial findings surrounding the potential significance of indicator sources (manufacturers) on pH measurements obtained with the sulfonephthalein indicator m-cresol purple. HPLC analyses were used for comparative assessments of impurities in m-cresol purple obtained from a range of manufacturers. Results indicate that m-cresol purple from different manufacturers, and perhaps from different batches of the same manufacturer, have different types and quantities of light-absorbing impurities. Impurities can contribute to pH offsets as large as 0.01 pH units. The pH offset caused by impurities decreases with decreasing sample pH. Indicators can be purified using preparative HPLC. Until purified indicators and refined indicator calibrations become available, we suggest that investigators should reserve some portion of each indicator batch for comparison with the properties of purified indicators.

    http://discover-decouvrir.cisti-icist.nrc-cnrc.gc.ca/dcvr/ctrl?action=shwart&aix=7&aid=7160664

    Since Byrne is a co-author, one might suppose they saved the indicator…for the 2006 cruise. How does one correct for the 1991 cruise?

    You also say:
    “The paper shows that they were able to get similar precision (long term ±0.0032, short term ±0.0012) with their modification of the technique.”

    My point all along is that both technique should give “similar precision”. The problem is that +/-0.0032 is based on 1 sigma (lots of details shown) and +/-0.001 is…what? (no details shown.)

    And finally, perhaps you’re right about my financial analyst analogy. A more apt analogy would be if my financial advisor comes to me and says “OMG! Your net worth last quarter fell by $0.03 +/-$0.01! What’s more, I have a financial model that says this will accelerate in the future! You and your family must change your lifestyles NOW and you have to give me more money to so I can stay on top of this and so that I can study it further. No question allowed!”

    Always like to have the right analogy.

  204. ZP- nice job. I too am concerned with this method. In fact there may be no more important issue with respect to ocean acidification than the uncertainty associated with this method. You simply cannot make any claims using hard data with respect to ocean pH as a result of anthro-CO2 unless you accept Byrne’s analytical assertions. I would add one more thing to your comment– what one is able to achieve under best practices in a lab is always better than what can be achieved in the field – especially an insitu devise.

    Byrne holds patents on both the instrument and method– not sure of (or if) the financial incentives to him and or the university if pH spectrphotometers become a “must have” piece of equipment.

  205. re Pat Moffitt: June 22, 2010 at 6:33 pm

    Hi Pat. There is an element of truth in the statement made by your commenter. Simply feeding the starving is fine as a temporary measure, but if all you are doing is creating more mouths, and are not able to support them indefinitely (which will eventually be the case), then you may well just be creating more deaths.

    The only long term solution, always, is for societies and groups to have the means to support and develop themselves. People will generally find a way to accomplish that if not interfered with, but the current demonization of carbon has the direct effect of interfering with such efforts in a massive way.

    What is insidiously effective in making basic energy prohibitively expensive, from the point of view of a eugenicist, is that you don’t have to ‘target the undesirables’ or actively become involved with them in any way. You just make it hard for them to survive, and they will eventually not be there.

    I have friends who feel that this indicates cynicism on my part. They just cannot believe that other human beings would have such motives, nor actually attempt to carry them out. I understand their reluctance to believe this, but all you have to do is take the eugenicists at their word, and they have issued such statements of intent often enough, and publicly enough, to be believed.

    /dr.bill

  206. Dr. Bill
    I’m always a bit uneasy when the well fed opine on whether the starving should eat. I am a firm believer that the best population control comes from the creation of wealth. Wealth creation starts by freeing people from subsidence agriculture, fostering a “climate” where business can flourish and access to boundless supplies of energy. (The anti green approach.) I believe in mankind and I believe in hope. (Also anti-green)

    As one example- it is though that some 70 million starved under Mao -who actively sought to engage the US in nuclear war. China is now fed and beginning to attain wealth. While some current events say China is still a threat- it is not the same threat as posed by Mao. No Korea is another Mao example. History shows too many wars started by hungry people.

    [REPLY - Gosh, yes. ~ Evan]

  207. re Pat Moffitt: June 22, 2010 at 10:24 pm

    I agree wholeheartedly with all of that, Pat., and I hope you weren’t referring to me as one of those who “opine on who should eat”. The official “green line” is about as odious to me as you can imagine.

    /dr.bill

  208. Read through all the whole thread and replies – absolutely enjoyed the cut and thrust and the counters, ocean acidification is a topic that is presently being used in the Australian science and political debate. I do have a concern about the way it is being presented.

    I wondered if those who are passionately for science and have expertise in the field have any such (or similar) concerns at the way this paper is being put out to the general public.

    http://www.science.org.au/nova/106/106key.htm

    The paper says in part
    Acid test for the seas
    This topic is sponsored by the Australian Government Department of Climate Change.

    The basic facts on ocean acidification.

    Chemists have known for a long time that a beaker of water sitting in a lab will absorb carbon dioxide from the air and turn acidic. Would it happen at a larger scale? If we greatly increased the concentration of carbon dioxide in the world’s atmosphere, for example, would the oceans become a vast acid bath? What would be the ecological effects? Over the next century or so, we are going to find out.

    Increasing atmospheric carbon dioxide

    For more than two hundred years, the human race has been releasing large quantities of carbon dioxide and other greenhouse gases into the atmosphere. It has been doing this in two main ways: by burning fossil fuels, such as coal, oil and natural gas, and by clearing and burning vegetation, such as forests.

    Ocean acidification

    Not all the carbon dioxide released
    into the atmosphere stays there; some of it – about a third of total human-induced emissions – has been absorbed by vegetation during photosynthesis and a similar amount has been soaked up by the ocean. We’re lucky that it has, or global warming would be happening much more quickly than it is.

    The oceans are naturally alkaline, or basic, with a pH of about 8.2. When carbon dioxide dissolves in sea water it forms carbonic acid (H2CO3), which releases hydrogen ions (H+), lowering the pH and making it more acidic. Scientists estimate that the additional carbon dioxide in the atmosphere and the subsequent absorption of some of this by the oceans has lowered oceanic pH by about 0.1 units since 1750. They also estimate that the oceans will continue to absorb the excess carbon dioxide present in the atmosphere and that oceanic pH will fall by a total of about 0.5 units by the end of this century, bringing it down to about 7.7. This is still slightly basic – so we won’t be creating a vast acid bath. But the pH scale is logarithmic, which means that even a decline of half of one unit will mean a several-fold increase in the concentration of hydrogen ions. (there is more if you actually read the paper)

    My concern at the above – is this just political science being presented as a careful clever spin to aid the government justifying carbon capture or cap and trade, and is this a fair use the present position of scientific knowledge or is it just an aid to promote a form of post normal science or just propaganda.

    It gives me a very uncomfortable feeling. Any advice would be helpful thanks.

  209. KenB says:
    June 23, 2010 at 5:05 am

    If we left a glass of “distilled water” on the shelf it would absorb CO2 and pH would decline. Natural rain water as a result has a pH about 5.5 (Interesting to note when everyone was taught to fear acid rain that rain is always acid- there is no natural basic rain). The glass of water analogy is inherently flawed because the ocean is not distilled water but well buffered . (And you can have near shore surface water swings in pH over 0.5 units over the course of a day) Using this glass of water/CO2 analogy is inappropriate if not deceptive and says much about those pushing acidification.

    We have no ability- by testing- to say what the ocean pH was a hundred years ago. And as these discussions have shown it is doubtful we can measure any decline now and ascribe those changes to CO2. This is all being driven by model assumptions-and the assumptions are always in the direction the grant funding agencies want. Studying the possibility of ocean acidification is not what we are doing- researchers are funded by government agencies to assume acidification and demonstrate its impact. That is not science.

    The oceans have a number of very real problems- some like commercial overfishing- are fueled by government subsidies. (The answer to solving such problems are for governments to spend less money not more). Why believe government’s are concerned about acidification that may occur in a hundred years when they do not correct the most critical problems that we face NOW? A problem they fix by not spending money. For governments-problems are needed so they can spend money.

  210. Smokey says:
    June 22, 2010 at 9:54 am

    CO2,

    You may think that nitpicking everything said shows that you are intelligent and up to speed on the subject, but all it shows is insecurity covered up by ad hominem attacks [Monckton, etc].
    ——————————–
    Ad Hominem attacks; Al Gore et al? Pot calling the kettle? Let me know one day, do you fully believe Christopher Monckton’s every word? Perhaps better to leave me guessing.
    ——————————–
    Arbitrarily changing your original 10,000 year assertion to 20 million years is still cherry-picking. Using the time scale of the biosphere’s use of CO2 does away with the cherry-picking. I can provide you with charts similar to the one I provided up-thread, going back 4.6 billion years if it helps. They show that CO2 has been almost twenty times higher than today, in both hothouse and icehouse epochs, and during times when life thrived in much higher CO2 concentrations — without any runaway global warming.
    ——————————-
    The cherries are getting quite old. In your case older than the earth (4.54 billion years). It seems someone else picked the cherry; http://www.sciencemag.org/cgi/content/abstract/1178296 between 180ppm (glacial) and 280ppm (interglacial) There are many more studies, just Google them yourself. When life thrived under much higher CO2? Like microbe colonies 3.5 billion years ago?

    http://ris-systech2.its.yale.edu/paleo/pdf/Oldest_Fossil.pdf

    ————————–
    I stand by every statement I made, and while you demand citations [which I routinely gave], you provided none yourself, but only off the cuff opinions based on your scientific flawed assumptions.
    —————————-
    You referred to a graph, without any validating text. The graph wasn’t even related to the issue. As to the rest, an assumption on your part.
    —————————–
    For one example of many, you stated that: “…water vapour is not a gas, it is suspended H2O and has a cycle of hours or days.”
    In fact, water vapor is a gas. Since your level of understanding is so rudimentary and filled with misconceptions, I suggest you read the WUWT archives from the beginning, so you can have an intelligent conversation without making such basic scientific errors.
    ——————————–
    Sorry, I have better archives than WUWT. If water vapour is a gas, why don’t you call it water gas. Water’s natural state is liquid and in all meteorological references it is referred to as vapour.

    We can treat it two ways; 1- when the gaseous phase is in equilibrium with the corresponding liquid or solid, or
    2- when we wish to emphasize that we are talking about the gaseous phase, even though for some reason the condensed phase is considered “normal”.

    Thoughtful experts refer to gaseous H2O as “water vapor” even in situations where it is nowhere near being in equilibrium with any condensed phase. Meteorology is one example, where we speak of various amounts of water vapor in the atmosphere. Astronomy is an even more extreme example, where congregations of cosmic H20 molecules are called interstellar water vapor. Since the dawn of time, these particular H2O molecules have been nowhere near saturated vapor pressure. Nobody ever speaks of water gas.
    Technically and officially, “water” refers to the H2O molecule in any phase (gas, liquid, or solid) … but unofficially by long tradition “water” connotes the liquid unless otherwise specified. Water is normally a liquid.”

    Hence water vapour is called a greenhouse gas, because all other gasses in the atmosphere are gasses (in their natural state). It would feel awkward if we called it a greenhouse vapour

  211. CO2 has wasted a lot of typing, only to show that he does not understand very basic physics. It is universally accepted within science that water vapor is a gas, by definition.

    CO2 states that “…water vapour is not a gas, it is suspended H2O”, then he goes into somewhat convoluted explanations trying to justify his assertion, such as, “Nobody ever speaks of water gas.” Actually, some folks refer to water vapor a “greenhouse gas,” even though the atmosphere is not a greenhouse. But water vapor is a gas, not ‘suspended’ droplets of moisture, as in fog.

    A simple search produces the following definitions of gas and water vapor:

    Define “gas”:

    • The state of matter distinguished from the solid and liquid states by: relatively low density and viscosity; relatively great expansion and contraction with changes in pressure and temperature; the ability to diffuse readily; and the spontaneous tendency to become distributed uniformly

    • A fluid in the gaseous state having neither independent shape nor volume and being able to expand indefinitely

    • Natural gas: a fossil fuel in the gaseous state; used for cooking and heating homes
    wordnetweb.princeton.edu/perl/webwn

    Define “water vapor”:

    • The invisible, gaseous state of water
    resweb.llu.edu/rford/docs/VGD/GSLVT/gslglossary.html

    • Moisture existing as a gas in air
    http://www.nachi.org/glossary/w.htm

    • Water in its invisible gas form
    wxlegacy.0catch.com/terms/vocabulary.htm

    • Water in a vapor (gaseous) form
    http://www.newschannel10.com/Global/story.asp

    • Water in the form of a gas
    http://www.nhcs.k12.in.us/staff/bburson/webcreation/science/ch10d.htm

    This is not nitpicking. Misunderstanding so basic a concept displays a profound lack of education in science. Anyone who believes that water vapor is not a gas needs to re-visit 5th grade science, and that is no exaggeration.

  212. KenB says:
    June 23, 2010 at 5:05 am
    ……..
    My concern at the above – is this just political science being presented as a careful clever spin to aid the government justifying carbon capture or cap and trade, and is this a fair use the present position of scientific knowledge or is it just an aid to promote a form of post normal science or just propaganda.

    It gives me a very uncomfortable feeling. Any advice would be helpful thanks.

    It’s a fair presentation of the science, the speculative part is prefaced by “scientists estimate” which seems reasonable.

  213. I have been away for a few days and haven’t been able to follow the thread. But, thanks to ZP for a very comprehensive and well laid out analysis of the limits of precision of a pH measurement. It was done far better than I could

    As an approximation, 1mV equates to 0.01 pH units, so to have an accuracy of 0.0001 pH units you would need to detect a difference of one-hundreth of a millivolt. Drift and stability are shown to four decimal places, but the electrodes don’t read to that.

    The calibration for this paper uses a spectrophotometric method, but that brings in other problems, which ZP does a good job of detailing also. Looking at my indicator reference book, the visual transition intervals for meta-cresol purple are only given to one decimal place, does anyone have them quoted with greater precision ?

  214. Phil. says:
    June 22, 2010 at 2:04 pm

    Pressure obviously supercritical, the temperature of the CO2 would have to be over 31ºC to be a supercritical fluid.

    It should be at least that when it is being emitted by a volcanic vent.

  215. Z says:
    June 23, 2010 at 12:21 pm
    Phil. says:
    June 22, 2010 at 2:04 pm

    “Pressure obviously supercritical, the temperature of the CO2 would have to be over 31ºC to be a supercritical fluid.”

    It should be at least that when it is being emitted by a volcanic vent.

    Yeah you’d think so, it’s subsequent history would be interesting since you’d have simultaneous cooling an dissolution (both ways).

  216. PAEH says:
    June 23, 2010 at 11:36 am
    I have been away for a few days and haven’t been able to follow the thread. But, thanks to ZP for a very comprehensive and well laid out analysis of the limits of precision of a pH measurement. It was done far better than I could

    As an approximation, 1mV equates to 0.01 pH units, so to have an accuracy of 0.0001 pH units you would need to detect a difference of one-hundreth of a millivolt. Drift and stability are shown to four decimal places, but the electrodes don’t read to that.

    The method doesn’t use electrodes, it’s entirely spectrophotometric.

  217. Bill S says:
    June 22, 2010 at 11:23 am

    Oh dear, 200+ posts and no one commented on the title? Love the reference to “The Electric Kool-Aid Acid Test”–haven’t thought of it in a long while, but it’s one of my favorite books. Thanks again, Willis.

    I was beginning to lose hope that someone would notice …

    w.

  218. Ken Peterson says:
    June 22, 2010 at 2:45 pm

    Since you’re citing and interpreting Monterey Bay Aquarium data, I contacted one of our water quality researchers. Here’s what they have to say:

    If you add a basic trendline to the data set, it actually shows that there is a longterm decrease in the pH of our intake water. The slope of the line is −4.1283e−006. They can use the data, but it actually does more to reinforce ocean acidification using it at face value.

    Ken Peterson, Communications Director, Monterey Bay Aquarium

    Thanks, Ken. So the slope is -.000004 pH units per year, and the water quality folks say that shows a longterm decrease? Someone should tell them about the concept of statistical significance, as that slope is most assuredly not statistically different from zero.

    w.

  219. Z says:
    June 22, 2010 at 1:33 pm

    This means that for the top 800 metres of the ocean, where the majority of the oceanic life exists, the human induced change in pH was -0.013 over 15 years. This was also about the amount of pH change in the waters around Hawaii.

    Now, remember that the difference in pH between the surface water in Hawaii and Alaskan is 0.50 pH units. That means that at the current rate of change, the surface water in Hawaii will be as alkaline as the current Alaskan surface water in … well … um … lessee, divide by eleventeen, carry the quadratic residual … I get a figure of 566 years.

    You didn’t just divide one into the other did you? It’s a log scale, and that just doesn’t work that well.

    Yeah, I thought about that, but pH varies linearly with pCO2. Assuming that the driving force is the change in atmospheric CO2 (and thus pCO2), and that the increase in atmospheric CO2 is linear, we can divide one into the other. Or at least that was how my logic went, let me know if I’m wrong.

    w.

  220. ZP says:
    June 22, 2010 at 5:28 pm

    The authors of this paper are definitely overstating the certainty of their data. The spectrophotometric procedure may have an internal precision of around 0.001 absorption units, but the total reportable uncertainty must be determined by propagation of the error throughout all calculations performed. …

    ZP, thank you for a most lucid and readable explanation of the issues involved in the determination of the pH. I had suspected their data as soon as I read the claims of accuracy to 0.001 pH units, but knowing nothing of the question of the accuracy of pH meters, I put it down to my naturally suspicious and unbelieving character.

    So thank you for restoring my faith in the fallibility of scientists, much appreciated.

    w.

  221. Phil. says:
    June 24, 2010 at 7:13 am

    Willis Eschenbach says:
    June 24, 2010 at 2:40 am

    Yeah, I thought about that, but pH varies linearly with pCO2.

    Willis, according to:

    http://www.sciencemag.org/cgi/content/full/286/5447/2043a#E1

    [H+]^2 is proportional to pCO2 so that would give pH varies as ln(√CO2)
    Might not make much difference for small changes in CO2 of course.

    Yes, curiously I used that same paper as a reference. You are correct that pH varies as ln(√CO2). However, over the range in question, the graph in the paper shows that the relationship is only trivially different from a straight line.

    Thanks,

    w.

  222. Willis Eschenbach says:
    June 24, 2010 at 10:38 am
    Phil. says:
    June 24, 2010 at 7:13 am

    Willis Eschenbach says:
    June 24, 2010 at 2:40 am
    …….
    “[H+]^2 is proportional to pCO2 so that would give pH varies as ln(√CO2)
    Might not make much difference for small changes in CO2 of course.”

    Yes, curiously I used that same paper as a reference. You are correct that pH varies as ln(√CO2). However, over the range in question, the graph in the paper shows that the relationship is only trivially different from a straight line.

    Indeed, the advantage of using logs!
    Implies that a factor of 2 in pCO2 would give an increase of 1.4X in [H+], -0.15 in pH.

  223. Phil in your reply, you deliberately ignored the first sentence at the start of my last paragraph. So I will repeat it here :

    “The calibration for this paper uses a spectrophotometric method, but that brings in other problems, which ZP does a good job of detailing also. ”

    You obviously intended to misrepresent my statement. I also notice that you have completely ignored the entire post by ZP, which specifies with great clarity and articulation, why the pH cannot be measured to 4 decimal place precision either by electrodes or spectrophotometry. Why have you chosen to do this ?

    To recap from ZP, even if they were to use a spectrophotometric system for detection of [H+] based on theoretical pKa calculations on a dye, at some point in the real world they would have to compare the theoretical prediction against an actual electrode reading. And the point of my last point was that to do that to 4 decimal place precision (aside from all the other practical limitations that ZP discusses), the electrode would have to be capable of accurately and precisely distinguishing one hundredth of a millivolt. If you can’t compare your theoretical prediction to an actual reading then you can’t claim the precision.

    I will not comment on your debate about the certainty that the same batch of dye could have been used 15 years apart to avoid the issue of differing impurities affecting the accurate repeatability, or accepting corrections that are greater than the stated precision, I believe other commentators have shown how erroneous those beliefs to be.

    But, I will go back to one of you earlier posts where you pulled some information from an internet site, carbonic acid is , well an acid, whereas the bicarbonate ion will buffer saline in the alkaline region above pH 7 !

  224. There’s an interesting article I stumbled across today, which bears directly on this issue and supports my contention that the so-called “acidification” is a non-issue.

    Also:

    Pat Moffitt says:
    June 24, 2010 at 6:04 pm

    Willis you missed the “your either on the bus or off the bus” Acid Test comment

    Sorry, I saw it but didn’t comment on it because I’m either in my mind or out of my mind …

  225. Please can someone help: I’m just trying to work out how Willis calculated the number of years for Hawian waters to reach Alaskan pH levels based on the quoted rates of change. Is the following correct:

    The existing Hawaii to Alaska pH levels are quoted as 8.05 to 7.65. A pH difference of -0.4. Due to the logarithmic scale this corresponds to a factor of 10^-0.4 = 0.398 reduction in alkali concentration.

    The GRL report claims the 15-year man-made pH change is -0.012 (= factor of 0.973)

    OK. Now how to calculate the number of years ‘Q’ to reach Alaskan levels.

    Is it 0.973 ^ (Q/15) = 0.398 ?? In which case, by interating on my calculator I get Q = 33 x 15 = 495 years?

    Next question: Is it reasonable to assume each yearly reduction will be a constant factor – or would it be more accurate to assume a fixed reduction every year.

    eg. (Q/15) * (1-0.973) = 0.398 so Q = 221 years ??

    Either way I agree it’s not much to worry about when you consider the effect of deepwater mixing.

  226. ukipper says:
    July 1, 2010 at 1:18 pm

    Please can someone help: I’m just trying to work out how Willis calculated the number of years for Hawian waters to reach Alaskan pH levels based on the quoted rates of change. Is the following correct: …

    Your calcs are correct ukipper, my numbers were slightly wrong. As you point out, it makes no difference to the conclusions.

  227. 06 de julio de 2010
    Andrea Mitchell interviews Jane Lubchenco,Administrator of the National Oceanographic and Atmospheric Agency, at Aspen Institute Ideas Festival 2010.
    Gulf Oil Crisis: Collision of Technology and Biodiversity

    min 49.25 Jane Lubchenco says:

    Oceans are becoming more acidic because much of the co2 that we have pumped into the atmosphere is being absorbed by oceans and it makes them more acidic. They have become 30 % more acidic in the last 100 or so years than that they were before.

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