A Neutral View of Oceanic pH

Guest Post by Willis Eschenbach

Following up on my previous investigations into the oceanic pH dataset, I’ve taken a deeper look at what the 2.5 million pH data points from the oceanographic data can tell us. Let me start with an overview of oceanic pH (the measure of alkalinity/acidity, with neutral being a pH of 7.0). Many people think that the ocean has only one pH  everywhere. Other people think that the oceanic pH is different in different places, but is constant over time. Neither view is correct.

First, here is a view of a transect of the north Pacific ocean from Alaska to Hawaii, with Hawaii on the top left, Alaska on the top right, and depths shown vertically. ocean ph along transect

ocean ph along transectFigure 1. Variation in pH by latitude and depth. The graphic is taken from a previous post of mine regarding oceanic pH.

Note that in Hawaii, the surface pH is above 8.05, and in Alaska the surface pH is below 7.7 … and despite that, the marine environment in Alaska is much, much richer in life than the Hawaiian marine environment. This underscores a simple fact—alkalinity is hard on living creatures, much harder than acidity. For example, if you want to dissolve the victim of your latest murder spree, you’d use lye (a strong alkali) and not sulfuric acid (a strong acid). [Well, maybe not you, but your neighbor about whom everyone always said “He always seemed like such a nice man …]

Now, neutral on the pH scale is 7. In line with our bodies’ poor tolerance of alkalinity I just mentioned, we often eat things like lemon juice, which has a pH of around two, which is neutral minus five pH units … whereas the most alkaline foods that we can tolerate have a pH of around eight, which is only one pH unit above neutral.

That’s why fish often have a slimy kind of mucus that covers their entire bodies … to keep from slowly dissolving in the slightly alkaline ocean. And it’s also why a slight trend towards neutrality in the ocean is not worrisome in the slightest.

Having seen the spatial changes in pH from Hawaii to Alaska, Figure 2 shows the temporal changes in oceanic pH in a variety of other marine environments.


oceanic ph in various locationsFigure 2. pH in different marine environments. DATA SOURCE: PLOS

Figure 2 shows not only the mean pH in these environments, it shows the variation in each environment over time. Note that while the open ocean shows a narrow pH range, a number of marine environments show a wide range over time. Coral reefs and kelp forests, for example, show a large variation in pH, which can be as large as a full pH unit in a single month. To quote from the underlying source for Figure 2:

These observations reveal a continuum of month-long pH variability with standard deviations from 0.004 to 0.277 and ranges spanning 0.024 to 1.430 pH units. The nature of the observed variability was also highly site-dependent, with characteristic diel, semi-diurnal, and stochastic patterns of varying amplitudes. These biome-specific pH signatures disclose current levels of exposure to both high and low dissolved CO2, often demonstrating that resident organisms are already experiencing pH regimes that are not predicted until 2100.

So we’re already experiencing what is supposed to terrify us, the so-called “acidification” of the ocean that is predicted for the year 2100.

For a real-world view of what that difference in variation means over time, Figure 3 shows the data from the Hawaii Ocean Timeseries (HOT) project, and the data from the Monterey Bay coastline.

surface ph measurements monterey bayFigure 3. Surface pH measurements from HOT open ocean and Monterey Bay upwelling coastline. The Hawaii data shows both measured pH (black) and pH calculated from other measurements, e.g. dissolved inorganic carbon (DIC), total alkalinity, and salinity.

As you can see, it’s nothing for any one of the thousands of different species living offshore from me to go through a large rapid swing in pH. It doesn’t seem to bother them in the slightest, they’ve been doing it for millions of years. Not only that, but as you can see from the Hawaii data, the slow drop in alkalinity is gradually moving the ocean towards a more neutral condition, which living organisms don’t seem to mind.

All of which is why I say that the gradual neutralization of the ocean from increasing CO2 is meaningless. It’s also why I say that calling the process “acidification” is merely an attempt to increase alarm. What’s happening is gradual neutralization, at a rate of something like 0.018 ± .001 pH units per decade (mean of seven multidecadal pH datasets) … color me unimpressed.

So with that as prologue, let’s take a look at the oceanographic pH data which I discussed in my recent post called pH Sampling Density.  In that post I noted that there should be enough data in either the area around Japan or in the North Atlantic to form some idea about the usability of the dataset. To begin with, here is the Atlantic data, along with Hawaiian HOT data and the Monterrey Bay data.

surface ph measurements atlantic and hotFigure 4. Atlantic pH measurements from oceanographic transects (blue circles), Hawaiian single-location HOT pH measurements (red-calculated, black-observed), and Monterey Bay pH measurements (cyan, with the standard deviations shown by whiskers). Black line is the expected decline in oceanic pH due to the increase in CO2. “Trend 1970 onwards” is the trend of the Atlantic oceanographic pH data.

There are several interesting aspects of this. First, the decline in the HOT measurements is close to the calculated decline due to CO2. Now, I have estimated this decline using the measured average changes in dissolved inorganic carbon DIC due to the increased atmospheric CO2. To do this, I’ve used the R code located here.

And while this is only an estimate, it turns out that it’s quite close to both the decline in the HOT and other multi-decadal single-location measurements cited above, and is also matched quite well by the trend in the Atlantic post-1970 oceanographic measurements of -0.019. It’s also worth noting that prior to about 1960 the calculated decline in pH is so small as to be almost invisible.

Next, Japan. This area has quite a bit more data, but like the Atlantic, unfortunately there is little data from about 1940 to 1960. Figure 5 shows the Japan data in the same format as Figure 4.

surface ph measurements japan and hotFigure 5. pH measurements from oceanographic transects off of Japan, (blue circles), Hawaiian single-location HOT pH measurements (red-calculated, black-observed), and Monterey Bay pH measurements (cyan, with the standard deviations shown by whiskers). Black line is the expected decline in oceanic pH due to the increase in CO2. “Trend 1970 onwards” is the trend of the Japanese oceanographic pH data.

Once again we see the same pattern as we saw in the Atlantic data, with an increasing trend in the latter years of the data, and a post 1970 trend of the same order of magnitude as the average of the seven multi-decadal studies cited above.

So there you have it. The oceanographic dataset confirms the gradual decline in pH, but doesn’t provide enough data prior to about 1960 to tell us much of anything. As usual, the problem is that the changes due to CO2 are so small that they are difficult to dig out of anything but the most accurate of datasets. This doesn’t mean that we can’t use the existing oceanographic measurements … it just means that we need to be cautious in their use.

Regards to everyone,

w.

AS USUAL: If you disagree with someone, please QUOTE THE EXACT WORDS THAT YOU OBJECT TO. Even with threading, it’s often quite difficult to determine what someone’s objection might be. Quoting their own words makes it clear just where your disagreement lies.

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264 thoughts on “A Neutral View of Oceanic pH

  1. Hey, thanks for the tip on the Lye….
    Next, Japan. …. .., unfortunately there is little data from about 1940 …probably got blown up

    Willis, here’s the link to Hawaii….it’s a mess….

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

    and the support info that spells out the mess….

    http://www.pnas.org/content/suppl/2009/07/27/0906044106.DCSupplemental/0906044106SI.pdf#nameddest=STXT

    basically..they ended up with a huge sine wave….just like temps….depending on where you “cherry” pick your start and finish…you can show a huge increase in pH….neural…..or a decline

    If they had started around the late 1970’s and ended around 2004…and “if this trend continues” you would have your lye………..

    • Perzactly!
      A good red wine has a pH of around 3.5 and rainwater around 5.8. I know of none who have forsaken either.

      • This is a myth. Quicklime preserves remains. Chemically dissolving a body completely is quite difficult.

        I recommend wrapping in a blanket, soaking in kerosene and burning. The blanket acts as a wick for the rendered fat which then burns long enough and hot enough to reduce even bones to ash.

  2. I really enjoyed reading this.

    Ocean acidification by absorbing CO2 is a typical alarmist ploy. Take a mildly interesting phenomenon, then spin it wildly with the sole intent of scaring the poo out of the uninformed lumpen proletariat.

    It was a relevation to me that we, and most of the Earth’s creatures, are more tolerant of acid than of alkali environments.

    We also have to remember that acids, such as sulphuric and nitric, are produced my man in huge quantities, much of which ends up in the oceans.

  3. Don’t get carried away with the pH of foods analogy. Our stomach acid is far lower pH than any food. Of course alkaline foods would be more disruptive to consume.

    Quite agree that Ocean Neutralisation is not a concern though.

    • Thanks, MCourtny, but that just demonstrates my point. Exposure to something as alkaline as our stomach acids are acidic would dissolve the tissue in short order … we are far more tolerant to acids than to alkaline substances.

      w.

      • For the most part, a very nice article.

        “Exposure to something as alkaline as our stomach acids are acidic would dissolve the tissue in short order”

        I don’t know about that. Ammonia cleaning solution is something like pH 12. Very irritating, but it won’t dissolve your skin.

        “… we are far more tolerant to acids than to alkaline substances.”

        In food yes, since stomach fluids are quite acidic.

        Organisms evolve to adopt to their environments. If they are evolved to an environment at pH 8.0, within certain variations, a sufficiently large, rapid change to either the mean or the extremes is likely to be disruptive. The ability to tolerate transient variations does not mean the organism can adopt to a permanent variation of the same magnitude. Many trees and animals live in an environment that has temperatures below freezing several months a year. Permanent temperatures below freezing would kill them.

        There are good reasons to be skeptical of claims that a small drop in ocean pH will be a catastrophe. But that does not mean that a sufficiently large drop in pH won’t radically alter the oceans.

      • Willis – they actually sell drinking water with a ph of 9.5. It tastes good and is supposed to have some interesting medicinal properties. Ray Kurzweil swears by it.

      • Mike M., ammonium cleaning agents are considered moderately base at 11 or 12 and have small amounts of ammonia.

        Every month, new studies are released which show that marine organisms are far more adaptable to changes in pH and temperature than was formerly thought. A favorite mantra among Alarmists are that coral reefs are disappearing because of pH and temperature changes and we’re all going to die. That’s where my skepticism has already kicked in.

        Most of the damage man has done to the marine environment has nothing to do with CAGW or neutralization. Crusading about “ocean acidification” or neutralization caused by man takes attention and funding away from real environmental concerns with respect to all bodies of water. That makes it more than a waste of time with limited financial resources. Socialists need to be cut off at the knees, financially (i.e. no more taxes). Scientists simply need more time and a lack of media attention before the human race takes any action in the above areas. Neither idea seems likely.

  4. Just a ‘few’, ‘small’, issues, as usual, as follows:

    How many of these values have been correctly normalized to 25 C (as pHs should properly be to allow valid comparison)? I have personally interviewed young grad students freshly off an oceanographic vessel who were found to have been accumulating such data without using a recently calibrated in situ temperature probe on the same platform. When questioned they revealed profound ignorance of the fact that pHs need to be temperature-normalized to allow a valid comparison.

    How many of these values have been accumulated with a pH probe which had been specially manufactured for a (variable) high, ionic strength – in particular for sodium? It is well known in chemical engineering, hydrometallurgy etc., but strangely not environmentally or oceanographically that in a high Na+ (and NaSO4- ion pair) species environment a ‘regular’ pH probe is also responding to a small but significant (in terms of the above analysis) extent to the high free Na+ .

    How many of these values have been accumulated with a pH probe which had not been two-point calibrated with say buffers at 7.000 (or 6.88) and 9.00 etc., the very same day? The mV slope through the 7.0 to 8.5 needs to be checked at least daily and most probes – especially the more modern gel-filled varieties typically degrade noticeably slope-wise over less than a year.

    As a 66 year old geochemist who has truly ‘seen it all’ in respect of the quality and deep thought content of field parameter pH, EC, DO etc., monitoring over a 40+ year career (particularly in the Gen X & Y period ;-), I’d hazard a guess that the above analysis and its inferred trend could well be as deeply flawed historically and methodologically as e.g. the many AGW proponents claim Beck’s analysis of the whole suite of pre-IR atmospheric pCO2 values is. And please….don’t get me started on ice core CO2 methodology…..

    • This brings to mind the siting issues with surface station temperature values. We have numbers. Those numbers might be valid for within 10 feet of the station. But valid for global temperatures?

      PS We use 7.00 and 10.00 buffers 3 times a day with a 4.00, 7.00 and 10.00 done twice a week. But we only deal with fresh water.

    • @Steve Short

      you wrote: “And please….don’t get me started on ice core CO2 methodology…..”

      But, please, DO get started on this topic! Since you have obviously great experience in analysis quality control, it would be quite interesting to hear your opinion about this subject, which is one of the main foundations of the orthodox IPCC views in AGW…

      Thanks in advance for your answer to my request!

      • Hey Mosher…..is that raw data after BEST adjusted it “is the best”…..or is that raw data after GISS adjusted it “is the best”….or is it raw data after step-wise adjustments “is the best”.
        Because I am seeing less and less “raw data” used by the alarmist brood.

      • But Mosh…the raw data from an observation is both the Ph AND the temperature…then one normalizes it…but if the normalization algorithm is incorrect, and if you dont have the raw data, you will never get another shot at correcting your manipulation. In this case, the raw data, that is both Ph and temperature, is superior to the result of the normalization alone, reported as if it wasnt subject to some massaging before being reported.
        Raw data should always be preserved, and the normalization algorithms should be rational, repeatable and open to inspection and critique.
        Your post are often obtuse and tedious, relying of obsfucation and equivocation, two rhetorical techniques beneath you.

      • All raw data should be retained and reported. In the case of pH readings, GLP requires (at a minimum) that the person reports both the pH and temperature.

        If one is going to compare pH readings, then one must first understand that pH represents the hydrogen ion activity not concentration. The hydrogen ion activity will change with a change in temperature for several reasons including the activity coefficients and dissociation constants are both temperature dependent.

        As a simple example, consider pure water. The pH of pure water is 7.00 only when the temperature is 25 °C. If we lower the temperature, then the measured pH will actually increase as shown in this link. This means that what we call neutral pH depends on the temperature of that solution.

        As Steve states, there are a lot of potential pitfalls in the area of pH measurement, especially when one is attempting to draw conclusions on small changes in pH. Reporting all raw data allows for a peer to be able to recreate and rigorously review the analysis and conclusions drawn. Reporting just the pH is insufficient for accomplishing this task.

    • The Station Aloha have been adjusted to 25 C: both the unadjusted and adjusted data are there in the file. Most of the ocean pH measurements are likely full of the kinds of problems Steve Short describes. The sites like Station Aloha were established to produce data that account for such things so that they can be used for valid comparisons.

    • I could not agree with you more. pH “trends” are meaningless absent a discussion of measurement uncertainty.

    • Steve, exactly. The (apparent) increases in reported SST should show a very small increase in pH. Moshe is being a bit sarcastic about “normalizing” because he thinks its analogous to the fiddling that is done to the temperature record (time of day reading and station moves are legitimate but the continuous, ongoing changes and this automatic temperature shift point correction(?) are not – the temp can shift). I would do however agree with Moshe’s point, though. Simply take the pH as it is AND record the temperature – they are related variables.

    • Modern pH measurements are taken using spectrophotometry (+/- 0.001 pH units) or ion selective electrodes +/- 0.01 pH units). Temperature correction is a feature of pH electrodes, not of the [H+] ion concentration. Still, part of the measurement protocol is to either do the measurement in to temperature controlled cell or to correct electronically for the temperature for the measurement.

  5. Willis, from your earlier pH density piece it looked like the gridspace in Red Sea off Jeddah is around 8.19 or closer to Hawaii than Alaska. We dove there and with some Aussies, who had also dived along Great Barrier Reef, and they thought the corals and fish life was extraordinary. I did too. Went out handline fishing and caught buckets of good grouper – what they call nigel.

    So, not the same species and maybe not the biodiversity of Alaska waters?? but still amazing. or life adapts . . .

    • Bubba:
      For some reason barracuda school in the Red Sea, and nowhere else that I know of. Did you notice that phenomenon?

      • There’s a species of Barracuda present off the West Coast of the US that schools and is fished as a sport fish. The fish are rather small — 2 or 3 kilograms (4 to 6 lbs) as I recall, but it’s been a long time. Perhaps I misremember

    • Red Sea is definitely an eye-opener. Wouldn’t guess it was relatively so alkaline if you listened to the alarmist assumptions. Interesting contrast to the none-too distant Mediterranean, where to my casual observations, both diversity and productivity of marine life seems to decrease from west to east, co-incident with decreasing alkalinity (?anybody point to confirming or contrary data on this). However I doubt that pH has much at all to do with it, and more to do with availability of nutrients (and possibly, in the shallow waters, oxygen). The Med opens to the Atlantic via narrow straits at Gibraltar, and you see quite large differences in the marine life even from one side of the Rock to the other. My own take is that significantly large changes in pH may indeed have an effect on marine systems, favouring some species/assemblages over others, and we may even, locally, be able to observe those changes, but that nature is way more than capable of ensuring that major deleterious effects will not occur.

      • Sorry – silly second sentence from me. Willis’s map shows high pH at the extreme N. end of the Red Sea (the touristy bit) but the most,still very rich, is relatively more acid. Confusing, those colours, eh?

  6. Perhaps the optimum pH for marine life is closer to the numbers you show for the Alaska environment. Perhaps some of the ocean’s waters becoming less alkaline is a good thing.

    • This is already proven by the very rich and thriving sea-life during the jurassic and cretaceous eras when there was about 4 – 5 times so much CO2 in the atmosphere than today. Why else are the lime-stone layers from this eras so mighty (e.g. Cliffs of Dover) and contain lots of corals and others sea-life fossils ???

    • The abundance of sea life is tied closely to the availability of nutrients, such as iron and phosphorus. Those are provided by upwelling and by the outflows of rivers, both a which probably lower the pH. But it is the nutrients, not the pH, that is key.

      For the most part, biological productivity in the oceans is very low, since most parts of the near surface oceans are starved for nutrients.

      • OK, but don’t forget: CO2 can not only reduce the pH of the sea water somewhat but is – first and foremost – a vital nutrient for all kinds of algae which are one foundation of the food chain in the oceans. In this double role it can improve sea-life not only by its influence on pH…

  7. The consumption of alkaline foods is very important for the health of the body. Our bodies are basically alkaline in structure, Our blood has a PH of about 7.458 and if it varies more than .10 up or down, we are in deep trouble. Our body fluids can vary in PH from 4.0 to 8.5 without great harm, but with a more acid environment in our body fluids, we are asking for diseases and organ failure over time. Acidosis of the body is a good way of increasing the risk of cancer and other life threatening events. I don’t know about the dafe PH of the oceans, but the balance of PH in the body is very important.
    Charlie

    • Not that long ago I pointed out that blood acidosis could be a life-threatening condition, with the diagnosis threshold being an arterial pH of 7.35. The Big Hint being that deceptively small-sounding numerical differences can’t be naively dismissed out of hand. And that acid/alkaline have traditional use as relative terms in science, not just as absolute terms.

      pH is important in the oceans, there have been so-called coral reef “bleachings” when pH has dropped below levels they’re used to. No one size fits all, different species in different environments have adapted to their local environments. Maybe they can adapt if the changes are gradual enough, maybe not. I chalk this one up to one of those things we don’t want to figure out empirically; lotsa people depend on reef ecosystems for food.

      • From the Victorian government site (AUS) on pool safety “If the water pH is higher than 8, anyone who swims in the pool is at risk of skin rashes, while a pH of lower than 7 can sting the swimmers’ eyes.

        More relevant is the recommended parameters for aquariums. http://www.liveaquaria.com/PIC/article.cfm?aid=89
        8.0-8.5 for coral reefs. The trend of -0.02 per decade might cause some grief to coral reefs growing in marginal areas in 100 years time but the ranges above suggest that they can cope until the population adapts to thrive.

        The acidifying oceans scare started in the late 90s due to a drop of 0.1 from pre-industrial times. The above plots suggest that the only drop has occurred since IPCC times. Not necessarily people being deceitful but I can see a researcher getting a high result and deciding to re-calibrate the probe, while thinking ‘bloody ocean acidification’ if its a low reading.

    • Brandon Gates January 2, 2015 at 9:05 pm Edit

      Not that long ago I pointed out that blood acidosis could be a life-threatening condition, with the diagnosis threshold being an arterial pH of 7.35. The Big Hint being that deceptively small-sounding numerical differences can’t be naively dismissed out of hand.

      Thanks, Brandon. Actually, the Big Hint is that deceptively small-sounding INTERNAL pH differences can be significant. As you say, a slight change in your INTERNAL blood pH can make a huge difference to your health.

      However, that means nothing regarding the current subject of discussion, which is the EXTERNAL oceanic pH differences. For example, humans swim equally well in Alaska and Hawaii, which are different in pH by 0.3 pH units … because the EXTERNAL oceanic pH has virtually no effect on our INTERNAL blood pH.

      w.

      • Humans do not swim equally well in Alaska and Hawaii. That was probably propaganda from the Alaskan Tourist Board.

      • I recall that when you hold your breath, the buildup of CO2 lowers the blood pH, for which the body has a sensor, and that prompts you to breathe (that choking sensation). Overbreathe, and the lack of CO2 raises the pH, and that makes you light-headed, so that slows your breathing.

        That’s sort of a workaround for the body’s lack of an oxygen sensor.

      • Willis,

        However, that means nothing regarding the current subject of discussion, which is the EXTERNAL oceanic pH differences.

        Thank-you, that’s a fair point. We do already know that various locations in the oceans have thriving marine populations and also show widely ranging pH concentration on an annual, seasonal and even daily basis. Organisms living in those environments have adapted to those local conditions. The concern is that movements in average pH will change the extremes in ways which stress keystone species, such as corals, which will then negatively affect other species in some locations. In this usage, oceanic pH, like GAT, is a yardstick. Both global and local uncertainties abound. We don’t know. Our not knowing is a risk in and of itself.

        We do know that there have been pH excursions which stress reef systems (coral bleaching) so there is some fair amount of concrete observed risk already in evidence. Those things have already occurred at the “minimal” (and controversially uncertain) pH changes already observed. Could there be other reasons for those things? Yes. Could these things have happened before at higher pH levels and we have not observed them? Yes.

        As someone who is not a marine biologist nor oceanographer, I’m loath to second-guess those who are. A healthy amount of skepticism, no problem. But in the end I am inclined to trust the experts in the field on these matters, and thus far what the research is saying is that, yes, lowering pH by such small amounts is already causing issues.

        Hence my blood pH analogy.

        The other point of that argument being: blood acidosis occurs in humans at a pH of 7.35, which as “everyone knows” is basic.

      • Brandon Gates January 5, 2015 at 6:41 pm

        We do know that there have been pH excursions which stress reef systems (coral bleaching) so there is some fair amount of concrete observed risk already in evidence. Those things have already occurred at the “minimal” (and controversially uncertain) pH changes already observed.

        Thanks, Brandon. Do you have a citation for the claim that changes in pH have bleached coral reefs? I haven’t seen any, but the world of published papers is a big place …

        Thanks,

        w.

      • Willis,

        Sure, you bet. K. R. N. Anthony et al. (2008), Ocean acidification causes bleaching and productivity loss in coral reef builders, open access: http://www.pnas.org/content/105/45/17442.full

        Tank experiment in the lab so they could control for temperature, nutrients, etc. Some interesting stuff about why bleaching happens generally — temperature excursions and other things can do it too, it’s not that corals are “bleached by acid” which is obviously what most folks would think on hearing it. The expected things like calcification rate are in there and some interesting stuff on symbiosis with other species, metabolic pathways, etc.

        Oh hey, we’ve got a model for that: http://www.biogeosciences-discuss.net/11/187/2014/bgd-11-187-2014.pdf

        Ruben van Hooidonk, et al. (2013), Opposite latitudinal gradients in projected ocean acidification and bleaching impacts on coral reefs, open access: http://onlinelibrary.wiley.com/doi/10.1111/gcb.12394/full

        More models, but this time using CMIP5 output against prior corals research for impacts assessment, and a scan through the references shows a pretty good cross-section of all things coral … ah bingo:

        Neil C. S. Chan and Sean R. Connolly (2013), Sensitivity of coral calcification to ocean acidification: a meta-analysis: http://onlinelibrary.wiley.com/doi/10.1111/gcb.12011/full

        Not free, but the supplimentary info has a spreadsheet full of the studies used in the meta analysis: http://onlinelibrary.wiley.com/doi/10.1111/gcb.12011/suppinfo … 25 studies total, with duration of studies ranging from 3.8 years down to 2 hours. The nutritional note for that short study says, “Not fed”. No kidding …

      • Sorry, Brandon, but the first study is nothing but a lab study, and jacking CO2 in the lab means nothing about how coral reacts in the real ocean for a number of reasons. The coral reef is not just the coral itself, it’s all of the reef creatures as well. For example, coral tends to die if it is not regularly grazed by parrotfish … and as far as I can see, they didn’t include parrotfish in their experiment. Nor did they include many of the other hundreds of organisms that make up a healthy reef. It’s one of the big problems with studying a complex ecosystem—you can’t just grab one piece of it and study it in the lab.

        However, there’s a much larger problem. That paper also says:

        Previous studies of CO2 enrichment and warming in corals and algae have not observed a bleaching response (22, 23). One explanation is that this study used a higher natural irradiance (average of ≈1000 μmol photons m−2 s−1), which is a key bleaching agent in corals (24), thereby bringing organisms closer to their bleaching thresholds.

        Say what? Previous studies “have not observed a bleaching response”, which agrees with what I’ve read. So since they couldn’t get the appropriately frightening results, they’ve added extra light to get the corals to bleach … and you actually believe this kind of stuff? Hang on, let me figure out how to convert their units …

        Great googly moogly, 1000 μmol photons m−2 s−1 is equivalent to an illumination of sunlight of no less than 4,500 W/m2 … which is more than four times the maximum intensity of sunlight at the tropical surface. Are we supposed to be impressed that the corals bleached under that onslaught? Four thousand plus watts per square metre, that’s hilarious. I can see why they expressed it in μmol photons m−2 s−1, so people wouldn’t immediately just point and laugh. My friend, you need to become a whole lot more skeptical, and actually look at the studies that you are recommending.

        The second study, as you point out, is a model study of a model study … sorry, not interested. Those are just guesses by people with an axe to grind. That study claims that:

        Of all reef locations, 90% are projected to experience severe bleaching annually by 2055.

        I’m interested in actual observations, not computer-based hyperbole. Corals evolved during the Paleozoic, when CO2 levels were two or three times as high as today. So I’m afraid that some geek sitting at his computer model predicting gloom and doom is less than convincing when we know they’ve survived those CO2 levels in the past …

        Your third citation is to yet another computer model of a reef … boooring. We have no evidence that any of these models have been tested, verified, or validated. And it is most probable that they were built by true believers. You know, the kind of believers who add super-bright lights to bleach corals and then claim it’s from CO2. You seem impressed by such models. Me, I know that they are not tested as extensively as the models we use to run our elevators … not impressed.

        I’m a man who wrote his first computer program more than fifty years ago. After a lifetime of both writing and using a host of computer models, I’m clear that a computer model is only a fast way to calculate the understandings, misunderstandings, and prejudices of the modeler who wrote the program.

        Finally, your last reference says nothing about bleaching that I can find. Also, I am always very suspicious about “meta-analyses”. If the effect is so weak that it cannot be demonstrated by a single analysis, stacking up a bunch of individually inconclusive analyses doesn’t make it any stronger. In addition, it is quite common for such analyses to be beset with bad statistics, as well as post-hoc study selection. Meta-analyses are a pit of snakes, you need to look very, very closely at such results.

        In closing, let me say that many people misunderstand coral bleaching. It is not the death of the reef, not by any means. Instead, it is one of the many ways that the reef adapts to changing conditions. When those conditions change enough, the symbiotic coral organisms die off (bleaching) and are replaced by other organisms which are adapted to the new conditions. I’ve seen the process in action diving on the reefs after thermal bleaching, and it’s surprisingly quick—a few seasons, and you can’t tell that the corals were ever bleached.

        My best to you, and thanks for the citations, they provided some needed humor in an otherwise serious evening. 4.5 kilowatts per square metre of light and I’d bleach in a few moments …

        w.

      • Willis,

        Sorry, Brandon, but the first study is nothing but a lab study

        Why would you apologize to me for something I told you myself?

        It’s one of the big problems with studying a complex ecosystem—you can’t just grab one piece of it and study it in the lab.

        I guess you missed the lecture when isolating variables was in the lesson plan.

        Previous studies “have not observed a bleaching response”, which agrees with what I’ve read.

        One wonders what the surrounding text said …

        I’m interested in actual observations, not computer-based hyperbole.

        Oh I agree, human-generated hyperbole is far superior.

        So I’m afraid that some geek sitting at his computer model predicting gloom and doom is less than convincing when we know they’ve survived those CO2 levels in the past … I’m a man who wrote his first computer program more than fifty years ago.

        [note: carefully edited for clarity]

        Corals evolved during the Paleozoic, when CO2 levels were two or three times as high as today.

        Good grief, you missed the lecture on mass extinctions too? Join the Holocene aready, science has come a long way since the Cambrian explosion ended very badly at the end of the Permian.

        I tell ya’, some days I do wonder if my faith in Darwin is misplaced.

        Your third citation is to yet another computer model of a reef … boooring.

        Ok, how do you figure out whether some future event will happen or not?

        We have no evidence that any of these models have been tested, verified, or validated.

        What kind of evidence do “we” require? To what mailing address does one send such evidence? How fast do “we” need it? How long will “we” require to reivew and accept said evidence and accept or reject it? Have “we” ever heard of peer-review?

        Do “we” understand that major scientific journals with lots of money and prestige at stake do not publish crap on a whim?!?

        I guess “we” really just don’t get it after all. Color “us” shocked.

        And it is most probable that they were built by true believers.

        As opposed to false believers.

        By the way, what is the definition of a “true believer”? Are they second-cousins of True Scotsmen? And since your’re so big on evidence, how is it you come to your conclusion that this particular batch of researchers “probably” fit that definition? I mean … really … a proper skeptic such as yourself wouldn’t just believe any old thing without — what’s that word you guys ironically (mis)use all the time — proof would you?

        Finally, your last reference says nothing about bleaching that I can find.

        You missed the lecture on synthesis too I guess. The key words are from the abstract are: aragonite saturation state; carbonate chemistry; CO2; coral calcification; coral reefs; pH, all of which you’ll find in the other literature I cited. Try reading for comprehension, and you just might figure out what the dealeo behind the bright lights is.

        Also recall, if feasible without doing too much damage, what you pointed out in your opening remarks; these are complex organisms in a complex enviroment, and that means understanding as many as possible observables so as to be able to make more accurate predictions. Otherwise known as doing good science. Perhaps you’re familiar with the concept?

        pH ain’t the only measurable quantity here, it just happens to be the one you’re apparently hyperfocused on at the moment. Capice?

        Also, I am always very suspicious about “meta-analyses”.

        They’re controversial to be sure. Publication bias is probably the biggest knock against them in my view.

        If the effect is so weak that it cannot be demonstrated by a single analysis, stacking up a bunch of individually inconclusive analyses doesn’t make it any stronger.

        Where is it written that the only reason to gather multiple samples is to manufacture a pre-conceived conclusion? Not in any stats book I’ve ever studied, and I’m surely no expert at that any more than I am at marine biology. What do the authors themselves say about why they did their analysis?

        It is not the death of the reef, not by any means.

        Guess whose turn it is to cough up the citations?

        My best to you, and thanks for the citations, they provided some needed humor in an otherwise serious evening.

        So you read peer-reviewed literature for laffs, and I read this blog for the same. Suddenly the world begins to make sense to me.

        4.5 kilowatts per square metre of light and I’d bleach in a few moments …

        You know, that was exactly the idea. Pretty smart these people who actually know what they’re doing, aren’t they?

      • Geez, Brandon, get a grip.

        You argue about every nit-piickin’ little thing, parsing it just the way you want it. I’d be surprised if everyone shares your personal concerns. I’ve certainly had worse said about me. It’s part of the deal with commenting.

        At one point you ask:

        What kind of evidence do “we” require? [to validate a model]

        How about predicting a series of events based on your model’s algorithm? Predict when, for example, global warming will commence, and at what annual rate? Or will it be global cooling? If your model works, it might predict that, too.

        Tell us the year those events will begin. Will global T go up, or down? What will the trend line look like?

        Simples …if your model can predict — and if it can’t, what good is it?

      • dbstealey,

        You argue about every nit-piickin’ little thing, parsing it just the way you want it.

        The obligatory lead-off ad hom, with an amusing nit-pick about picking nits.

        I’d be surprised if everyone shares your personal concerns.

        The appeal to popularity.

        I’ve certainly had worse said about me. It’s part of the deal with commenting.

        The ad hom, reprise but with contrast.

        At one point you ask:

        What kind of evidence do “we” require? [to validate a model]

        Finally addresses an actual argument …

        How about predicting a series of events based on your model’s algorithm?

        … but does so by asking a disingenuous question …

        Predict when, for example, global warming will commence, and at what annual rate?

        … then asks about a continuous physical process as if it were something that has only two possible states …

        Or will it be global cooling?

        … tosses out the opposite logical possibility as if it inherently carries an equal probability of happening …

        If your model works, it might predict that, too.

        … proposes a model with dissociative identity disorder …

        Tell us the year those events will begin.

        … goes back to inventing imaginary boundaries …

        Will global T go up, or down? What will the trend line look like?

        … asks again what he very well knows has already been answered many times by the IPCC …

        Simple …if your model can predict — and if it can’t, what good is it?

        … and for the grand finale, forgets that “all models are always wrong” is nigh indisputable, unavoidable truth, and that “but some are useful” is a matter of subjective opinion.

        Yet again fails to provide the one objective thing which would settle this argument in his favor: a “skeptical” model which is more skillful at prediction than anything produced by numerous consensus climate teams.

      • Gates says:

        The obligatory lead-off…

        Which does nothing whatever to falsify it. But clearly, the truth hurts enough to complain about it.

        All these LO-O-O-O-O-NG replies to simple facts mean nothing. They are obfuscation.

        Almost always, the truth is simple:

        No alarmist predictions have ever happened, or global warming stopped many years ago, or there are still no measurements of AGW.

        And so on. There is no need to publish a long mish-mash of pixels, unless you’re trying to cover up simple truths.

  8. In chemistry class they told us that human blood has buffers in it to damp out acids/bases, and there are 20:1 more buffers to handle acids because most chemical reactions in the body produce acids. Sea creatures probably the same.

  9. Willis, did you account for the oversampling for depth > 0 from 1980 onwards? This tends to skew the results as pH decreases with depth.

    Here is what I get with depth = 0:

    When I used depth = 0 data, with obvious outliers filtered, I got this result:

    And when I took the average, variance and deviation for depth = 0, I got this:

    • There were also there results:
      https://wattsupwiththat.com/2014/12/30/ph-sampling-density/

      Berényi Péter
      December 31, 2014 at 8:58 am

      A preliminary look at the data shows beyond doubt, that ocean pH is decreasing indeed, at a rate of -0.002±0.038/decade. In other words, it is absolutely stable.

      (5×5 deg grid boxes, monthly averages, trends computed for grid box/month combinations with at least 15 years of data – 382 such boxes were found)

      If only grid boxes with at least 20 years of data are considered (204 items), ocean pH trend is -0.002±0.031/decade, therefore the null result is reasonably robust.

      Berényi Péter
      December 31, 2014 at 9:18 am

      Yes, trends are only calculated for the same month of the year in each grid box.

      Berényi Péter
      December 31, 2014 at 9:29 am

      I have given a try to grid box / month combinations with at least 30 years of data (81 items). The result is +0.003±0.026/decade, therefore the null result is incontrovertible.

      • The Station Aloha data that Willis posted earlier show a trend of -0.0171 ± 0.0018 per decade.

        “The result is +0.003±0.026/decade, therefore the null result is incontrovertible.” No, that just means that those data are not good enough to detect the trend.

      • Mosh, you are a bitter man.. I always wondered why you “ran off the rails”. Turns out that “Best” was really the “Worst” for you. Get a grip on it man…..Ya wanna be a star, Put on your “Big Boy” boots and stop crying like a baby when criticism comes your way…what a whiner……….otherwise, reinvent yourself to avoid being a broken record.

      • @Steven Mosher: Please don’t act obtuse. Of course you don’t throw the raw data away, but you do discard outliers sometimes and you do normalize against another property that affects the data of interest in order to apply reasoned analysis.

        Your posts have become less worthwhile over time, and are now simply a waste of bits.

      • Steven Mosher January 2, 2015 at 5:34 pm

        filtering outliers!!!!
        na, use the raw data, you cant throw data away.

        SteveS January 2, 2015 at 9:53 pm

        Mosh, you are a bitter man.

        Thanks, SteveS, but you are missing the humor entirely … understandable, as Mosh subjects his posts to extreme data compression. Let me try to explain.

        People tell Mosh all of the time that Berkeley Earth and other temperature groups should “use the raw data”, and complain bitterly when they do anything at all to the original observations … but now, folks are complaining because people ARE using the raw data when they should filter out the obvious outliers. (Bear in mind that the total range of reported pH values in the dataset goes from 0 to 24041 …)

        So Mosh is taking the mickey out of those folks, by pointing out that indeed, often the raw data simply cannot be used as it comes in over the transom.

        Unfortunately, he left off the [sarc] and [/sarc] tags …

        All the best,

        w.

      • Willis

        You conclude your interpretation of the post from Steven Mosher by saying

        Unfortunately, he left off the [sarc] and [/sarc] tags …

        Sorry, but the series of complaints at the post from Steven Mosher are because there is a deeper problem than missing tags.

        I suspect your interpretation of Mosher’s post may be correct, but it is your interpretation and it may or may not be correct. Importantly, as gary turner says, posts from Steven Mosher are usually “obtuse”, and this problem is compounded by the habit of Steven Mosher responding with abuse when questioned as to what he meant.

        Steven Mosher has a degree in English so there is no excuse for the obtuse posts which he normally provides and which waste space in threads. I support the advice to Steven Mosher provided in this sub-thread by SteveS.

        Richard

      • An excerpt from Steven Mosher’s biography, which throws some light on his comments above.

        He attended Northwestern University where he graduated with honors and BA’s in both English Literature and Philosophy.

      • It used to be usual to show the data that you dismissed as an outlier. I think that people want to see from BEST, say, the average over 50-100 periods for only stations opened for the full period. No homogenising, gridding or anomalies not because it would represent the correct global average but it would give people an idea of how much the data has been adjusted. Noisy and with no obvious cooling trends and people might accept the adjustments better.

        The raw data for the few individual stations that I’ve checked doesn’t leave me feeling confident of the final result. And as I have pointed out before, BEST has monthly averages with half a degree uncertainty for my area 15 years before any data was recorded for a 200 km radius, and 50 years before BOM think that the records are reliable.

        The town Mildura has a station, Mildura Airport going back to earlier than 1947 when it opened. No station change indicated between 1947 and 1950 with just QC failed marked (I wonder why). A lot of data missing between 1950 and 1980 at the 7 stations less than 100 km away but break points of a tenth of a degree were identified and corrected?
        http://berkeleyearth.lbl.gov/stations/151971

        Warburton Range only has data for Warburton Airfield within a 200 km radius. Your QC says 0 months missing 10 days or more of data. BOM doesn’t have any monthly data for 1957-1964 and 1956 is missing a month. The only break point is in 1962 but the area, just Giles 208 km away, also shows cooler years like at Warburton in the maximum and minimum temperatures. How could you possibly find a break point?

        http://berkeleyearth.lbl.gov/stations/4663
        http://www.bom.gov.au/jsp/ncc/cdio/weatherData/av?p_display_type=dataGraph&p_stn_num=013017&p_nccObsCode=36&p_month=13
        http://www.bom.gov.au/jsp/ncc/cdio/weatherData/av?p_display_type=dataGraph&p_stn_num=013017&p_nccObsCode=36&p_month=13

      • I hope you aren’t contracting climatologist clinical depression that is spreading …dare I say alarmingly? …among those whose careers have been too rigidly and certainly attached to the MEME. You at least have English Lit to fall back on. Think of the older TEAM who have expended their entire careers chasing phlogiston while the whole science has begun to climb above their groove. Moshe, Moshe, you are a smart man. You didn’t have so much invested in the failure. You did the Best but get over it.

      • Willis gets it.

        of course people never ask how I switched from being a literature major to a data analyst/stats person

        this reading list might help

        http://www.amazon.com/The-Measurement-Meaning-Charles-Osgood/dp/0252745396

        and the relationship between information theory and the arts ( a great book for its time)

        so ya, when you start as a math and physics major and switch to the arts and then take a job in engineering.. the common thread is hard for stupid people to see.

        That common thread is information theory.

        So, when you see something uncommon in a data stream ( high entropy) that bit can be one of two things

        A) noise/outlier, get rid of it
        B) something VERY important.

        That’s why I scoff at people who think that Raw data should be worshipped. There are times when its junk
        and other times where its not.

        deciding when a bit is junk and when a bit is actually important information is not a simple thing.

        At any given time on on WUWT you will find people acting as if raw data is beyond reproach. You will
        find them berating folks who do adjustments. I like to take the piss out of these folks..

      • See above for why people have little faith in your ability to spot junk.

        Four break points and I can draw you an elephant. Five and I can make its trunk swing.

    • ferdberple January 2, 2015 at 3:00 pm

      Willis, did you account for the oversampling for depth > 0 from 1980 onwards? This tends to skew the results as pH decreases with depth.

      Thanks, Ferd. My results are solely from the surface observations (depth = 0).

      Also, using a straight line trend merely proves that you’ve used a straight line trend …

      w.

      • using a straight line trend merely proves
        ==============
        the point of the straight line was to show graphically how little variance there is in the result. If the data was truly poor quality it should be all over the place. the yearly average should show large swings above and below the the straight line trend.

        But it doesn’t. Which contradicts that assertion that the data is not of sufficient quality to calculate a trend. There is so little variance in the average year to year, in spite of the large number of points, taken at different times and places, by different vessels and different scientists. This is speaking volumes.

    • No, that just means that those data are not good enough to detect the trend.
      =============
      see the graph above fro 3:00 pm. the very low variance, typically well under 0.1 pH, tells us that the data is good quality. it isn’t that one can’t detect a trend, rather that the trend = 0 for the past 105 years.

      • Thanks, Ferd, but I can’t tell what you are doing. Are you really averaging the Caspian Sea with the mid-Pacific? If so, why?

        And are you averaging monthly or annually? Are you averaging the pH (wrong), or first converting it to H+, averaging, and then converting back to pH?

        Next, if the third panel above is the average, sd, and variance of the data in the second panel, I don’t see how that can possibly be true. You have data running from a pH of 6 to 10 … I’m not buying that the standard deviation of that data is a tenth of a pH unit.

        Finally, what’s with the miniscule scales? Looking at those teeny lines, anything is possible.

        Lemme take a look and I’ll see what my numbers say, but I can’t see any use in the kind of average you are doing. It’s like averaging absolute temperatures from all over the planet that are bunched up in space and time and expecting the result to mean something.

        w.

      • keep in mind we are only trying to see if the data is good enough to compute a trend. we are not interested in the actual pH of the oceans, so we don’t care what our numbers represent. so long as the underlying data is bound by the central limit theorem, to the extent that the process that generates the pH reading can be considered random as to location and season, then the result should be normally distributed, from which we should be able to make some determination of data quality.

      • OK, ferdberple, I’ve graphed your data (annual averages of all surface pH readings regardless of locations) in a more visible manner.

        The true linear trend could fall anywhere within the red lines. As you can see, this means that the trend could be up, down, or level … and there’s no way to tell.

        Which means that if we use all of the data, the result is not good enough to say anything about the true trend … but that’s no surprise. We’ve mixed up pH from alongshore, from upwelling zones, from mid-ocean, from inland seas, from enclosed bays, from everywhere.

        In addition, the sampling is bunched in time, so perhaps early in the period there are more samples from low pH areas, and late there are more samples from high pH areas, which would give a false trend … and as a result of all of those problems, the dataset is not useable as a whole.

        Which is not to say that subsets of the data are not useable. I’ve shown two such subsets above, the North Pacific and the area around Japan. These are at least relatively homogeneous. If you want to look at another one, I’d maybe look at the Caspian Sea, or perhaps another sample-dense area like the Black Sea or the Baltic, you might find something there.

        w.

      • It’s like averaging absolute temperatures from all over the planet that are bunched up in space and time and expecting the result to mean something.
        ============
        consider this:
        if one was to instead compute averages for each location, then compute anomalies, and then group all the anomalies according to a grid, that would work fine so long as your locations did not change over time.

        However, as we have seen with the weather temperature data, this leads to huge problems when stations move. The pH data is a moving station problem.

        An alternative approach is simply to consider each absolute temperature reading as a random sample on the surface of the earth. Given enough of these samples, to the extent that they can be considered random, that in itself should be sufficient calculate a pretty reliable average temperature of the earth, without any need to take location averages, compute anomalies, grid the result, make adjustments, etc. etc.

      • Willis, I have tried to convince Ferd with the same arguments, but it seems difficult to convince him. While his method doesn’t even work for temperature, where there are lots of stations, but a move of a few stations or a drop in number of stations (as was the case for the collapse of the USSR) will skew the result. It only works if you have a representative sample of the full population.

        In the case of ocean pH measurements it is even much worse, as the cruises over the years are one year east-west in the Pacific, the next year north-south in the Atlantic and there is a huge oversampling of the oceans below Japan, which shows a similar pH drop for fixed places:
        http://www.data.jma.go.jp/kaiyou/english/oa/oceanacidification_en.html

        There seems to be a firm increase of measurements in the Baltic Sea after 1990. Problem is that the Baltic is not open ocean, but a largely enclosed brackish water sea with a lot of runoff from rivers and only some ocean water coming in with the tides (the Mediterranean is even worse, but its salt content is higher than in the oceans due to evaporation).

        Anyway, have a look at the sample distribution in the critical years 1990-1995, when there is a (for open oceans) huge drop of 0.15 pH unit in a few years time, here compiled by Wallace:
        http://www.abeqas.com/ph-1990s/
        From 1990 on the measurements in the Baltic Sea increase, while at the same time the total number of measurements decreases. I am pretty sure things like that skew the pH record…

      • The true linear trend could fall anywhere within the red lines. As you can see, this means that the trend could be up, down, or level … and there’s no way to tell.
        ==============
        Yes Willis, a much closer result. However, even this tells us something. The red lines represent probability. And this probability is not uniformly distributed between the red-lines. Our answer is more likely to lie towards the mid-point, towards the trend-line between the red-lines, than it is to lie outwards towards the red-lines.

        So while our answer MAY lie anywhere between the red-lines, it is MORE LIKELY to be closer to the mid-point than it is to lie towards the red-lines. And, what is the mid-point between the red-lines? What does the trend-line tell us over 100+ years?

        The trend looks pretty well zero. Not negative. So, on the basis of probabilities, this data shows no evidence that ocean pH is decreasing. It holds open the possibility that ocean pH is increasing or decreasing, but the MOST LIKELY answer is that pH is not increasing or decreasing.

        And this is the information that was not presented to Congress.

      • While his method doesn’t even work for temperature, where there are lots of stations, but a move of a few stations or a drop in number of stations (as was the case for the collapse of the USSR) will skew the result.
        ==============
        ?? that doesn’t make sense. Or course it will work if there are lots of stations. Why say “but” after “stations”, except to try and follow with a rebuttal? Why rebut unless you know that the method wilt work but can’t bring yourself to admit it. Your words betray you.

        And of course any process that removes randomness can skew the result. In this the method is not alone. The brute force random method is like democracy. It is the worst possible way to calculate the average, except for all others.

        There are methods to restore randomness and reduce the uncertainty. However, I’m not paid by big oil or big government to do this. I have a day job and have simply tackled the problem as a concerned citizen. People that get paid to check that government officials are providing the full truth and nothing but the truth can take it from here

      • Ferdberple, you reported “The result is +0.003±0.026/decade”. So it can be anywhere from -0.023 to +0.029. That is completely consistent with the result of -0.017 per decade based on high-quality data. The data you have are not good enough to tell the difference between -0.017 and 0.000.

      • Ferd, when a lot of Russian stations were abandoned as the local people weren’t paid anymore. many of them were located in Siberia, known for their harsh winter conditions. By coincidence (?) “global” temperatures increased in that period.

        The pH data are already heavy weighted towards the oceans south of Japan. No problem in itself, but as the total number of sampling decreased and at the same time the sampling in the Baltic Sea increased (which has a rather low pH), the drop in pH for the total of the samples may be simply the result of the changes in number and place of sampling and not caused by a real global drop in pH.

  10. We are probably raised to be scared of ‘acid’. In the science lab, under the car bonnet, we are told to be careful where acid is found. Then warmists scare people with the ‘acidification of the oceans’ claim. The gullible know that must be automatically something bad.

    • Then warmists scare people with the ‘acidification of the oceans’ claim. The gullible know that must be automatically something bad.

      Just tell the gullible that the oceans are becoming less caustic.

      (Frankly, if I went to the beach I’d be more concerned with meeting Jaws than a 0.01 pH change.8-)

  11. Thanks Willis, very informative as always. When I scan all the “news” from MSM I get really angry with the endless barrage of climate fiction scare stories. I commented about ocean ph a few times and the CAGW crowd deliver insults faster than Don Rikkles could have! No discussing anything with that kind of vitriol.

  12. I really don’t think that you can just assume that sea life prefers lower pH just because you believe that there is more sea life in the waters around Alaska (a continental shelf environment) compared with Hawaii (an oceanic environment that just happens to have some large volcanos sticking up from the abyssal plain). Correlation does not prove causation. There are plenty of other factors that change between the two (temperature, turbidity, habitat). The mere fact that one is continental and one is oceanic may suggest why the Alaskan water is more neutral – freshwater run off which carries higher levels of nutrients).
    That said, your point that Sea life is adapted to higher pH is well made. Interestingly there is an anecdotal story in regards to Humpbacks in Western Australia. Apparently on their migration South along the coast they have been know to stop off for several days at the mouth of discharging rivers. I assumed that this was for anti fouling reasons, but it might also reduce stress.
    When we are arguing about the ability to lay down calcium carbonate, we should remember that human body is buffered very close to neutral and nobody has turned into a sack of jelly because of it.

    • Goldie January 2, 2015 at 3:21 pm

      I really don’t think that you can just assume that sea life prefers lower pH just because you believe that there is more sea life in the waters around Alaska (a continental shelf environment) compared with Hawaii (an oceanic environment that just happens to have some large volcanos sticking up from the abyssal plain).

      Sorry for the lack of clarity, Goldie. That wasn’t my meaning at all. What I meant was that sea live thrives both in Hawaii and in Alaska, and is by all appearances totally unaffected by differences in the alkalinity level.

      w.

      • Yes, I think that pH is a bit irrelevant except where it causes stress by being too high.
        If the oceans did ever actually turn acid – very hard to do given their buffering capacity, the first impact we might expect to see would be dissolution of inanimate calcium carbonate, not active living calcium carbonate. Apparently the CAGW doomsayers have forgotten that there is an enormous quantity of limestone or calcareous sandstone on our coastlines.

    • Goldie,

      At the risk of over simplifying, there are basically 2 different marine ecosystems. A food web adapted to upwelling zones and and a food web adapted to minimal upwelling. In the upwelling zones, diatoms comprise the major phytoplankton assemblages. In upwelling zones deep, acidic waters accompany the nutrition rich-oxygen poor water that are brought near the surface. So diatoms have siliceous shells that are impervious to changes in to any dramatic changes in pH typically observed in upwelling waters. Away from coastal and equatorial upwelling zones where upwelling has an insignificant impact on ocean pH, plankton with calcareous shells that would elsewhere be sensitive to upwelling predominate.

      Furthermore as we drop in depth and beyond the penetration of light required by photosynthesizing plankton, pH becomes increasingly acidic because respiration by decomposing bacteria dominates and releases more CO2 into the water. Organisms living at greater depths are more adapted to more acidic waters, and thus “prefer” lower pH. It is the organisms living at the boundaries of significant upwelling that can experience detrimental pH effects. Many bottom dwelling organisms can suffer rapid extermination during acidic upwelling events. However it is not clear to what degree pH contributes the die-off versus the accompanying lack of oxygen. Shellfish species have calcareous shells susceptible to acidification but they inhabit the sea floor bottoms and theoretically can be most susceptible to acidic upwelling. However one adaptive response is to simply burrow deeper into the sediment and “hibernate” during any acidic upwelling events.

      So in response to your reply regards “preferring lower pH”, there are indeed segments of the marine ecosystem that prefer low vs high pH. Upwelling zones exhibit dramatic increases in productivity that is exploited by specific species in the food web. However the degree of upwelling is periodic and those species undergo booms and busts.

      In low upwelling zones like the center of ocean gyres, very different species exist that are highly adapted to a less productive but more reliable environment. Those species are better adapted to recycling limited supplies of energy and plankton with shells that are more often calcareous and susceptible to acidification predominate.

      • Jim, thanks, I am not entirely unversed in this topic. However it seems to me that your discussion is actually suggesting that reducing pH in the oceans to any great extent might actually have impacts at the margins.

      • No I am not “suggesting that reducing pH in the oceans to any great extent might actually have impacts at the margins. ” even though thereis a connection. The biological pump will continue to keep waters more acidic at depth. Only less photosynthesis will pump less CO2 to depth. Seasons and cycles will vary the strength of upwelling and acidification along the coasts.

      • Jim, thanks for that overview. You say:

        In upwelling zones deep, acidic waters accompany the nutrition rich-oxygen poor water that are brought near the surface. So diatoms have siliceous shells that are impervious to changes in to any dramatic changes in pH typically observed in upwelling waters.

        Let me add that the big fear seems to be that a slight drop in pH will keep marine organisms from forming calcareous shells (shells made of carbon rather than silaceous shells made of silicon).

        For exhibit A in that category, may I point out that the humble mussel has a calcareous shell, and it not only lives along upwelling coasts where the pH is much lower than in the open ocean. It also lives in fresh water, where the pH is significantly lower than along upwelling coasts.

        How does it do that? Well, like all of life, it is internally capable of locally reversing the local external conditions. I’ve said it before, but it bears repeating:

        In the ocean, chemistry doesn’t rule life — life rules chemistry.

        w.

      • Jim, thanks for your comments. I enjoy it when a biologist brings sensible insights to bear.
        I would add radiolarians, a zooplankton with an external skeleton made of silica, to your illustration of the complexity of the aquatic stew of many flavors that is our ocean. Many of these organisms migrate vertically in the water column during the diurnal cycle and no doubt expeience pH variations on a regular basis.

      • Agreed and your saying is spot on: “In the ocean, chemistry doesn’t rule life — life rules chemistry.”

        Many organisms have adapted by internally controlling pH by sequestering carbonates, etc

      • Furthermore, there is a higher abundance of sea life around upwelling zones because these waters have more nutrients, e.g. iron, not because marine organisms prefer lower pH in general. Iron is generally the limiting component in ocean primary productivity.

  13. Thanks, Willis.
    “It’s also why I say that calling the process “acidification” is merely an attempt to increase alarm.”
    I used words to that effect at a NOAA “Open House” event last year. No wonder why I could not get a job offer from them.

      • Only if “better-fitting” means more willing to ignore inconvenient realities and to espouse alarmism …

        w.

      • Ha, that reminds me of the time I went for a lab tech job at the CRU.
        I wasn’t asked back for a second interview, without even a rejection. Yet, my qualifications and experience were well beyond that required.

        Perhaps, on reflection, they realised exactly what my scepticism implied? And they couldn’t face a serf questioning the neo-pause.
        I was early (asserts I)… sadly I can’t prove it.

      • MCourtney:
        Interesting. They have a lot to hide at CRU, so I imagine they are well-practiced at sniffing out the skeptical types.

  14. Caldeira and Wickett 2003 link the surface pH directly to atmospheric CO2, predicting a drop of about -0.4 pH units when the atmospheric CO2 hits 700 ppm. Since we should hit 700 ppm by 2110 (RCP6), they are proposing a somewhat faster rate of decline (about 0.3 units per century compared to your estimate of about 0.18 per century). But according to them, effects on marine life of pH at 7.6 will be dire. Their graph is fascinating to see, since if we went to 700 ppm in a mere 10 years, the ocean would follow suit instantaneously (right half of the figure).

    On the other hand, according to Dore et al 2009, we are already at 7.6 at a depth of 1 km.

    By the way, the 2.5-million observations of pH show a similar relation to depth as found by Dore:

    So I do think the dataset could be of some use assuming careful analysis and application of QA/QC techniques when available (e.g., concurrent observations of DIC, TA, pCO2 etc.)

      • heh heh. not to mention fitting an obviously nonlinear function to a linear regression. that works.

    • Decreasing pH with increasing depth is the opposite of what one would expect if human-emitted CO2 is the cause. If pH is decreased due to carbonic acid formed from dissolved atmospheric CO2, then one would expect pH to be lower and the ocean-atmopshere interface, i.e. the surface.

      • Except that you need to take into account what happens in the biosphere with depth… The above graphs show no trends, they only show a snapshot of the CO2 profile. Dissolved inorganic carbon is lowest near the surface, as that is where most of the calcifying organisms grow…

    • That red line on your last graph is meaningless. There is a rapid drop (0.35 over 1 km) in pH to about 1,000 m and then it levels off to about 0.1 over 5000 m.

  15. Phasinating phacts.
    Phraudulent phear-mongering phanatics phorcing phalse phacts phor phinancial phunding.
    Phools!

  16. Firstly, thanks very much for doing this work. Funny how a volunteer such as yourself is producing more useful data than the people paid to do it at the IPCC.

    I’m not a physiologist but I suspect that the information you have regarding pH in diet is a little off. For example, lemon juice is healthy not because its acidic, but because it produces an alkaline reaction in vivo. And while the body is fine with acidic foods (as long as the quality is good), it absolutely needs alkaline substances. Processed dairy milk is bad for your bones because a) it has little nutritional value, b) it congests the intestine and c) it is acidic.

    Soft drinks of any kind are disastrous because they are acidic, not just because of the sugar (or worse, the synthetic sweeteners). Soft drinks can be pH 2.5 or so while beer is merely 4 or so (and has fewer ingredients, therefore it’s ‘healthier’ than soda).

    • Your comment seems to confirm the placard I saw in a bar in Angle Inlet, Minnesota.
      It read:
      ” beer has food value,
      food has no beer value”
      cheers

    • Coke (and other cola brands) contains phosphoric acid, good to burn holes in your stomach (if you have a defect in the gland), other drinks usually contain citric acid but may be buffered with sodiumcitrate…

  17. Why should a pH-scare be different from a global-warming scare or from a high-voltage power line scare or from a radon-scare or from an ocean-rising scare? We don’t discuss good predictions with friends or neighbors: we mostly share alarms. Sharing of non-alarms is unethical. Sharing of false alarms should be unethical and punishable.

    • You forgot the “Ozone Hole”.
      The CAGW scare is fading with the public. Time to throw something else against the wall to see if it sticks.

  18. I have no reason not to accept the data that more acidic water s of Alaska has more wildlife than Hawaii’s more alkaline waters. However, several doctors told me that the human body, if more alkaline is more resistant to illnesses. And consuming lemon juice (an acid) will make the human body more alkaline and therefore more healthy. There seems to be a discrepancy on whether more alkaline is better or not to life… Can anyone educate me here?

    • Blood pH should be in the range 7.35 to 7.45. Some people believe that slightly on the alkaline side is better than slightly on the acid side. But I don’t know if there is any evidence for that. Unless, perhaps, you are prone to gout.

      The best pH for an organism is the pH for which that organism evolved.

      • The pH that is best for an organism is within the range of the pH in which that organism evolved.

        The term “evolution” is not compatible with the concept of a static world.

    • The gist of this story is that lemon juice (and other citrus) contain citric acid which comprises three chemical R-COOH groups. These are the acid termini of the citric acid molecule, with a tendency to donate their charged H’s (Protons) into the solution thus lowering the pH. This standard behaviour can be considered as an “overt” acidity and is easily measurable. It is also easily neutralised in the right circumstances. Adding lemon juice to gastric juice just means the gastric proton pump needs to work less harder to establish low pH for preliminary peptide digestion.

      Some nutritionists also talk about “acid-forming foods”. This is a “covert” acidity as it is not directly measurable by a pH meter. It results from metabolic combustion of fuel-rich foods having long carbon chains (fats, starches). When these chains are broken down and the individual carbons are oxidised during metabolism to release chemical bond energy for ATP formation, the eventual target product is CO2, which one can exhale. But on the way there, the oxidised carbons form intermediates which contain R-COOH acidic carboxyl groups. Generally speaking, Western diets consume a lot of starch and fuel rich foods, more than is needed so these acid metabolites can build up like a traffic jam. When balanced with vegetables that are rich in minerals and particularly mineral cations that can balance these acidic carboxyl groups, the “acidification” of the interstitial fluids of the body is kept in check. When the metabolic acids are in excess, “acid” deposts can accumulate around joints and in deep muscular tissues, leading to fascia and joint inflammation, stiffness and the like.

      Bear in mind that blood pH is tightly regulated within a narrow slightly alkaline range at about pH 7.4 If you force this toward the alkaline end, say by hyperventilating, you get a condition called respiratory alkalosis, and your head feels dizzy. So blood pH is always well buffered otherwise our brains would notice! But that does not apply to the rest of the body water that is more distal to the flowing blood, and which can locally attain hyper-acidity. Localised acid cannot be actively transported; you have to allow it to diffuse out. Drinking lots of water and good exercise will help. Acidity occurs particularly in regions that stagnate in water exchange rates due low blood flow and/or to sedentary practice,such as around the pelvis, due to lots of sitting at the computer desk. So there is a move now to drink alkaline water and consume barley and wheatgrass etc; to redress the imbalance we have acquired through over-eating of sweets and starches in particular. Vegetable and salad eaters (exclusing pasta, rice and potato) are less likely to get acidity hotspots than the potato and bread devourers.

      Experimentally I have found that eating a meal of a dark green leafy vegetable such as kale or bok choy in the evening induces a strong alkaline response the next day, measurable by a pH test of saliva. OTOH the more I deviate into bread and biscuits, the more acid my saliva becomes. Saliva is meant to be alkaline normally, which condition contends against mouth bacteria causing teeth and gum disease.

      Although lemon juice is overtly acidic, it does not fuel the body to any considerable degree; it has no significant “covert” acid value. On the other hand it does contain minerals as well, so that at the end of the metabolic train, it’s contribution is at least neutral,if not slightly alkaline. It’s a kind of paradox, in that we don’t expect this.

  19. Two important points are absent from this discussion so far concern WHY oceanic pH varies in the way that it does.

    The answer is simple: when photosynthesis & other life processes occur, CO2 and carbonic acid ions in ocean water are removed and transformed causing the pH to become more alkaline. In places where respiration dominates. CO2 is freed and lowers the pH.

    Life processes so dominate this equation that all the added atmospheric partial pressure of CO2 accomplishes is to fertilize the photosynthetic process.

    The second is that the buffering capacity of oceanic basins are so enormous that one would probably need several oceans of carbonic acid to titrate them down. Some one better than me can do the math to determine just how many oceans of carbonic acid it would take to eliminate inate buffering of ocean water and the megatons of calcareous bedrock in direct contact in their basins.

    The whole topic is Potemkin villages all the way down suitable for the marxists who attempt to perpetrate the fraud on “us poor suckers” /sarc.

  20. The problem with using all this “real data” is that it’s all over the place, it’s inconsistent, it varies from day to day, season to season, year to year, decade to decade and then it also varies from one location to another.

    No-one, even climate super-hero’s, can be expected to deal with all that variation & inconsistency. Climate scientists need nice clean data to work with, data which is properly aligned with their theories and the best way to obtain it is by modelling it. Once they have clean data it has the added benefit of highlighting what’s wrong with the “real data” allowing that to be corrected. Once the “real data” is properly corrected it can then be compared to the model data proving the models work.

    Why do people find that so hard to understand?

    • I assume you are not being facetious in your comment (?) If you are, my response here can be ignored. Variation (and inconsistency) is the spice of life. Nature very rarely does things in nice ordered ways according to human perception. This inconsistency of data,with the exception of human and equipment measurement errors, reflects its “realness” and is part of its charm. It means we can stay humble as we don’t know all the factors involved in a data point or cluster It may be nice to see some given data conforming to a perfect binomial probability density function, but this rarely, if ever happens. Error in technique is something we have to try to minimise, but then learn to live with. I disagree that clean data, as you put it, is that which aligns with a theory. The ab initio data is the data, and can never be “cleaner” than it is then (unless our measurement technology improves). Any data which is selected for its alignment to an expectation is in fact ‘dirty’ as it now has an added confirmation bias. Using bias to then haul other data into shipshape order simply introduces a toxic circularity and proves nothing.

      • Like +1, especially the phrase “toxic circularity”.

        Every time I see a Phil. post or a Joel Shore post, I think of Billy Preston’s “Will it go round in circles”. Unlike the deliberately broken wheel of Mosher and Stokes.

        In other words, I think jaffa was being facetious.

      • Agreed Phil, definitely facetious – in a tongue-in-cheek sort of way.

        And split into paragraphs too . . . .

  21. Willis, now that you’ve given us reason not to panic over ocean pH changes, maybe you, or someone else, can tackle the good news just out from NASA/Jet Propulsion Laboratory concerning forests and carbon dioxide. If tropical forests absorb far more carbon dioxide than scientists thought (1.4 billion metric tons of carbon dioxide out of a total global absorption of 2.5 billion) what does that mean? How does that compare to man-made emissions of carbon dioxide?

  22. First year chemistry and I was in the lab cleaning test tubes with concentrated 18 molar SO4, turns our there was a little water left in the test tube that I added the acid to. Small explosion resulting in minor acid burns to my face and eye which left me wearing an eye patch for a few days. Mrs K(short form for a huge Polish name ending in “ski”) told me how lucky I was for if it was [NaOH] I would be blind…smart lady..wore goggles after this…

  23. Lots of biochemists/biologists know that a pH change of 0.1 would generally not materially affect the cells that they grow in a laboratory, or their results (always with some exceptions). They (the cells) successfully manage their own internal pH which is usually a lower pH (more acidic, less alkaline/basic) than either pure water, the blood of the whole organism/creature, or the growth medium in which they are cultured.

    And these cells/creatures are often far more pH sensitive than most life forms living in the ocean that experience much larger pH changes every day.

    The CO2 “ocean acidification” scare was always a basic chemical and biological non-starter. That is why even the alarmists chose to focus on things like the inorganic chemistry of calcium carbonate (chalk), pretending that coral reefs will dissolve or not form.

    That is rubbish too. The coral reefs are made of vast amounts of solid calcium carbonates accumulated over thousands or millions of years. Like the surface of the White Cliffs of Dover, that calcium is not going anywhere quickly. It is right where it is needed.

    Which is why the educated alarmists retreated to the proposition that the new little baby coral polyps will not be able to form their little baby shells. Except that many corals do just that in more acidic environments. And so do little baby tiny creatures like E. Huxlei, one of the major photosynthetic calcifying organisms of the world’s oceans. They actually grow thicker coccoliths with increasing carbon dioxide levels. And ease off on their production of carbonic anhydrase which they use to harvest free carbon dioxide.

    You can chase the CO2 alarmists from pillar to post, and they will still come up with another junior-high-school-chemistry-level argument about why carbon dioxide is bad and not good.

    They won’t give up. But I don’t intend to give up either until I am dead or too ill to argue.

    • michael…they get glassy eyed when you tell them that organisms that lay down calcium or strontium skeletons….regulate their own CO2 internally…that’s how they do it

    • Michael. Your great comment captures Willis’s essay perfectly.

      You say (at the end) “You can chase the CO2 alarmists from pillar to post, and they will still come up with another junior-high-school-chemistry-level argument about why carbon dioxide is bad and not good.”

      Let’s face facts. Most AGW activists dropped Chemistry, Physics and Biology in favour of ‘Fashion and Fabric studies’, ‘Socialism and Politics’ and ‘Film, Drama and Theatre studies’.

      PS. Willis, this excellent post and the wonderful comments prove again just how educational WUWT can be for us all. Again, I’ve learned a great deal. Thank you.

    • Other high school subjects in favour of a basic grasp of High School ‘Chemistry’:

      ‘Finance and Accountancy’, ‘Dictatorship Studies’ and ‘Wizardry and Witchcraft’.

  24. Studying the Hawaii-Alaska transect, I am skeptical to the nth degree that overall ocean pH change can be determined to any degree of accuracy.

  25. Handle bleach or ammonia (Don’t mix them!!!) without gloves and your fingers will get slimy with dissolving skin.

  26. Actually there is reason to panic over ocean PH changes.
    Over a cosmic time scale the oceans will become like the dead sea from the accumulated alkali runoff from the land masses. That is unless there is a massive injection of acid into the oceans. There is not enough carbon on earth to do it.

  27. Willis wrote: “All of which is why I say that the gradual neutralization of the ocean from increasing CO2 is meaningless.”

    Rising ocean pH is NOT meaningless. The solubility of CaCO3 (calcium carbonate) depends on the concentration of CO3(2-) (carbonate ion). The concentration of CO3(2-) depends on pH and other chemical species associated with dissolved CO2 (H2CO3 and HCO3-). Calcium carbonate is essential to coral reefs and many other species including some types of plankton.

    I tried to work out some of the simpler chemical equilibria associated with carbon dioxide and calcium carbonate at Nick Stokes blog. http://moyhu.blogspot.com/2013/08/buffers-ph-and-ocean-acidification.html
    Anonymous August 10, 2013 at 3:37 PM

    My best estimate was that doubling CO2 would reduce ocean pH by 0.2 units at equilibrium in the presence of excess calcium carbonate (i.e. at a coral reef), but even this calculation is complicated and contains assumptions that may not be valid. Since CO2 has been rising 5% a decade, 15% (1/5 of a doubling) over the period in your Figure 3, the observed change in pH in Hawaiian is roughly consistent with my calculation. However, simple equilibrium calculations aren’t appropriate in complicated situations like upwelling in Monterey Bay. The ocean is not in chemical equilibrium; it is super-saturated in CaCO3 near the surface in many places. Temperature changes. The equilibrium changes with pressure/depth. (See calcium carbonate compensation depth).

    My favorite reason for not worrying about ocean acidification is that coral and other species evolved more than a 100 million years ago when atmospheric CO2 was higher it will be in 2100 without emissions reductions. CaCO2-based marine species thrived planet with 1000 ppm of CO2. And, as you point our, natural variability in ocean pH is large. Unfortunately, neither fact proves that important existing species are capable of rapidly re-adapting to a more acidic environment.

    • “Researchers at the University of Miami and the National Oceanic and Atmospheric Administration (NOAA) studied the effects of acidification on fish larvae – Rachycentron canandum. These large tropical fish are very busy and popular with anglers.
      With the method, computed microtomography (similar to that which is subjected to hospital patients), the researchers observed that in water at low pH fish develop a greater otolity (pebbles Labyrinthine) – included in the hearing – than animals from the waters of lower acidity. The weight of these structures made of calcium carbonate in the acidic water increased by up to 58 per cent., And a mathematical model for their functioning even indicated a 50 percent extension of the hearing.

      “Increased hearing sensitivity allows the use of it to navigate, avoid predators or communication” – said one of the scientists Sean Bignami of the University of Miami.”

      • Along with the pH data, has anyone begun to collect carbonate, bicarbonate and carbonic acid concentrations at the pH sample sites? Lots of things can effect pH and alkalinity besides them. If we build such a data base it might help show whether or not CO2 is the big bad boogeyman it’s being made out to be.
        (Just a layman’s thought.)

      • Also, how does the pH data compare with the CO2 measuring satellite data?
        Are ocean pH numbers lower in those higher CO2 areas?
        If CO2 is driving ocean pH lower then they should be.

      • Gunga, there are lots of measurements done for total carbon (DIC: dissolved inorganic carbon, the sum of free CO2 + bicarbonate + carbonate) many more than for pH, as that is easier to do and more accurate than pH measurements. It is possible to deduce the % of the different forms of carbon, if you know the pH via the Bjerrum plot:
        http://en.wikipedia.org/wiki/Bjerrum_plot
        All these data can be found in the same database as the pH values.

        Conversely if you measure total alkalinity of seawater and DIC, you can calculate the pH.
        Seawater reactions are quite well known and two variables + temperature and salinity are enough to calculate all other variables… That can help in looking for a trend over time when not enough pH samples were taken…

      • Ferdinand: Coral and other species use CaCO3 (calcium carbonate) to make their skeletons, not Ca(HCO3)2 (calcium bicarbonate). The reference you provided actually specifies that skeletons are made from CaCO3, but it uses an alternative mechanism for the formation of calcium carbonate from bicarbonate. This mechanism is probably relevant in the ocean where the pH is too low for significant amounts of CO3– to exists.

        Equation 1: Ca++ + CO3– CaCO3 Ksp = [Ca++]*[CO3–] = 5*10^-9
        Equation 2: Ca++ + 2HCO3– CaCO3 + H2CO3 + H2O Keq = [H2CO3]/[Ca++][HCO3-]

        If you apply Le Chatelier’s principle to Equation 2, it is easy to see why more CO2 will drive the equilibrium towards the left – towards less solid calcium carbonate and more calcium in solution. (If you apply it to Equation 1, lower pH lowers CO3–, allowing more Ca++ in solution.)

        The solubility product for Equation 1 and the equilibrium constant for Equation 2 are related by the first and second ionization constants for carbonic acid, K1 and K2:

        Keq = K2/K1*Ksp

        So it doesn’t make any difference whether one uses Equation 1 or 2 to generate calcium carbonate, one will reach the same equilibrium. The ocean, however, is not a situation where simple equilibrium considerations are always appropriate. Most of the ocean surface is supersaturated with calcium carbonate. See: http://www.jbc.org/content/58/3/649.full.pdf

        If you don’t believe me, please read further before spreading mis-information about the importance of calcium carbonate.

      • Frank,

        The sea pH and carbon equilibrium reaction changes are as you said, but as I said, that hardly influences the ability of the calcifying organisms to make their carbonate shells: carbonate is intracellular made from bicarbonate ions at their internal pH, not from carbonate in the oceans at the ocean’s pH.

        Of course if the pH of the oceans gets low enough to dissolve carbonates at near surface, then there will be a real problem, but that still is far away.

      • Ferdinand says:

        …if the pH of the oceans gets low enough to dissolve carbonates at near surface, then there will be a real problem, but that still is far away.

        How far away would that be, Ferd? In either centuries or millennia, please. Eons or Ages OK, too…

      • Ferdinand Engelbeen: “Of course if the pH of the oceans gets low enough to dissolve carbonates at near surface, then there will be a real problem, but that still is far away.”

        Much of the surface of the ocean is supersaturated with CaCO3, so all organisms need to do grow skeletons is catalyze the depositing of crystalline CaCO3. If they want to grow and keep skeletons in regions which are no longer supersaturated, that would require active transport of Ca++ and the expenditure of energy. The loss of supersaturated habitat could be the real issue.

    • The concentration of CO3(2-) depends on pH and other chemical species associated with dissolved CO2 (H2CO3 and HCO3-).

      If I’m not mistaken, the chemicals and their reactions with each other drive the pH, not the other way around.

      • Gunga, it is both: if you add a (stronger) acid like SOx (udersea volcanoes..) the pH lowers and more carbonates may dissolve and more bicarbonate and free CO2 is formed, which ultimately may escape to the atmosphere.
        If CO2 in the atmosphere increases, more CO2 is pushed into the oceans and the equilibria are pushed towards more H+, thus the pH lowers…

      • Ferdinand, thanks for both of your replies.
        I’m just a guy trying to apply what little I know to the CAGW induced hype.

      • Gunga Din: In traditional chemistry class, problems can be posed in a number of ways and with a number of assumptions. Most problems are chosen to be easy to solve. A simple problem might ask how much Ca++ can be present in solution below 0.0003 atm of CO2 at pH 8, without explaining how the pH is held constant at 8. For ocean acidification, a sensible question to ask is what happens when we double the amount of CO2 in an infinitely large atmosphere and when there is an excess of solid calcium carbonate present. This would be the situation for a shallow coral reef and possibly other places calcium carbonate is used for skeletons. This was the problem I tried to solve at Nick Stoke’s blog (see above) when I was unsatisfied with Nick’s analysis (:)). This problem has seven unknowns: CO2, H2CO3, HCO3-, CO3–, H+, OH-, and Ca++. (Eight unknowns, if you want to count CaCO3, which I assumed is present in large excess. All solids have a value of 1 in such equilibrium problems.) The pH (-log H+) effects the concentration of all of the other species and they all effect pH. For example, CO2 from the atmosphere becomes H2CO3, which changes pH; but also may precipitate CaCO3, which increases pH more that H2CO3 in the absence of Ca++.

        In the real world, however, there is far more CO2 in the whole ocean than the atmosphere. We burn enough fossil fuel every year to increase CO2 by 4 ppm (1%), but the equivalent of about 1 ppm “disappears” into the ocean (precipitated as CaCO3?) and 1 ppm disappears on land (dead plant material?). We have already burned enough fossil fuel to have doubled CO2, but some has already begun to equilibrate and we aren’t dealing with an equilibrium situation. “Toy problems” like the one in my calculation suggest principles that may be important, but they aren’t sophisticated enough to trust.

    • While i agree that acidification isnt a problem and have writtenon the subject many times. This post is correct the issuse raised isnt directly about pH its about carbonate and bicarbonate abundance.

      The majority of studies replicate open ocean simulations or what happens with an open air glass of seawater with changing conditions. Adding in a large caco3 buffer and supersaturation complicates matters. As does adaptive framework.

      Stating that alkalinity is harsh may be somewhat true but it dodges the oppositional argument in a way that im not comfortable with as a skeptic.

  28. What’s happening is gradual neutralization, at a rate of something like 0.018 ± .001 pH units per decade (mean of seven multidecadal pH datasets) … color me unimpressed.

    Me too. Although in retrospect this was not too surprising. Acid rains had joined Godzilla long before the heat and melt waters went missing.

  29. Should ocean pH mainly be coupled to atmospheric CO2? As far as acidification of ocean water is an issue, locally or generally, the culprit ought to be searched elsewhere than atmospheric CO2 rising from 250 ti 400 ppm.

    SOx, NOx, Cl- and others are produced in industrial processes and by volcanoes in significant amounts. They produce strong acids.
    Saturated solution of CO2 in freshwater, like our SodaStream bottles, holds pH 3-4.

    Combustion of, say, sulphur rich crude oil, may produce H2CO3, but also H2SO4. Which affects pH the most?
    Diesels and many other high temprature combustion also produces NOx., which adds to acidification.(besides, like CO2 it is also a fertilizer, essential to plants)

    Add some lemon juice to your SodaStrem and see what happens! Has none suggested that acidification of sea water might free CO2 to the atmosphere?

    • Philip T. Downman

      You ask

      Has none suggested that acidification of sea water might free CO2 to the atmosphere?

      Yes, I have been pointing that out for over a decade. Please see my post in another current thread and read my post from the past to which it links.

      Richard

      • ren

        I am not avoiding your post but I cannot address it because I don’t understand it.

        Richard

      • Yes, I see you have and acknowledge that. To further clarify what I mean is that CO2 could be freed from the oceans due to addition of H+ ions.(wherever they come from – industry, volcanoes, seasick guys vomiting HCl and so on)That’s how some buffer systems of the oceans work.

      • Philip T. Downman

        I agree what you mean but point out the issue of magnitude.

        Humans don’t emit much of anything.

        Richard

      • As responded a few times to Richard, if the pH is lowered due to stronger (volcanic, industrial) acids, that pushes CO2 out of the oceans and total carbon (DIC) decreases in the oceans.
        If CO2 increases in the atmosphere, more CO2 is pushed in the ocean surface, DIC increases and the pH decreases.
        Thus it easy to determine which one of these two is dominating by looking at the trend of DIC.
        In all cases where DIC is measured over time, DIC increases. A lot more easier to do and more accurate DIC measurements are performed than pH measurements.
        See: http://www.tos.org/oceanography/archive/27-1_bates.pdf

    • It appears that in the case of hot oceans (in summer) decreases solubility. The situation is different at the equator by sea currents which ensure the exchange of water and nutrients. This enables the use of CO2 dissolved in water by diatoms and algae.

    • The major ions such as Chloride and Sulphate are referred to as conservative species because of the constancy of their relative concentration in sea water. This was first observed by Marcet in 1819 and confirmed by the results of the Challenger expedition by Dittmar in 1889. Despite richard’s misinformation the ocean acidity is not a function of sulphate. Ocean acidity is controlled by CO2, the concentration of which depends on the atmospheric composition..

  30. Thank you Willis, its really nice you do these investigations!!

    Besides: I love your work on Corals, atolls and more, very interesting and useful too! Bad guys must hate you ;-)

    Kind regards, Frank

  31. As a regular non-commentator on the posts of this website, I am constantly amazed at the quality of the posts and the breadth and depth of the comments. and this one is a good example. i even find the mental exercise of deciding whether or not a comment should have had a sarc tag to be part of my daily enjoyment. My slight worry is that I have developed an addiction.

  32. Coral reefs and kelp forests, for example, show a large variation in pH, which can be as large as a full pH unit in a single month.

    Here is something else. Large PH changes over a few hours and days as large as those expected for the end of this century. Don’t loose any sleep over ‘ocean acidification’.

    Abstract – 2011
    Will ocean acidification affect marine microbes?
    ……….Useful comparisons can be made with microbes in other aquatic environments that readily accommodate very large and rapid pH change. For example, in many freshwater lakes, pH changes that are orders of magnitude greater than those projected for the twenty second century oceans can occur over periods of hours. Marine and freshwater assemblages have always experienced variable pH conditions. Therefore, an appropriate null hypothesis may be, until evidence is obtained to the contrary, that major biogeochemical processes in the oceans other than calcification will not be fundamentally different under future higher CO2/lower pH conditions.
    http://www.nature.com/ismej/journal/v5/n1/full/ismej201079a.html
    ———————–

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

    …..and (2) in some cases, seawater in these sites reaches extremes in pH, sometimes daily, that are often considered to only occur in open ocean systems well into the future [46]. …..
    DOI: 10.1371/journal.pone.0028983
    http://www.plosone.org/article/info%3Adoi%2F10.1371%2Fjournal.pone.0028983

  33. So what you appear to be saying, Willis, is that taking the known effects of CO² throughout the planet’s system it :

    Warms the planet and encourages plant growth

    reduces the alkalinity of the oceans and encourages sea creature growth

    So, overall then, it is a very, very dangerous chemical.

    Perhaps it affects climate scientist’s meagre brains.?

  34. The only site where one can calculate anything is Station ALOHA (22°45’N, 158°00’W) with its Hawaii Ocean Time-series (acronymed “HOT”, which is nothing but pure propaganda). Ocean pH variability is way too high anywhere else where measurements were taken.

    At this site in situ measured pH trend is -0.016 pH units/decade during the last 25 years.

    The only open question is why CO₂ partial pressure in sea water increases at a rate of about 20 µatm/decade at ALOHA while atmospheric partial pressure trend is 28 µatm/decade?

  35. This ocean pH debate is very interesting, and enlightening.

    What is totally clear is that the claim ‘the oceans have become 30% more acidic’ due to increased atmospheric CO2 is unreasonably alarmist and clearly intended to persuade the gullible that the oceans are becoming acidic enough to dissolve corals and sea shells, and anything else based on calcium carbonate. This alarmist deception amounts to a lie in my view.

    What is totaly depressing is to see scientific bodies promoting and justifying this lie. As in this NOAA ‘Primer on pH’. http://www.pmel.noaa.gov/co2/story/A+primer+on+pH

    They are very very naughty in there use of alarmist language and agruments. For example:

    “Why are scientists concerned about such a seemingly small change in pH?: Many organisms are very sensitive to seemingly small changes in pH. For example, in humans …a drop of 0.1 pH units in human blood pH can result in rather profound health consequences, including seizures, heart arrhythmia, or even coma (a process called acidosis).” [get in there with scary health stories. A change of just 0.1 pH unit – ie, like in the ocean – can cause all these terrible things. Omit to mention we can tolerate much greater ranges of pH in what we touch or consume, with no ill effect, and our own stomachs create a mucher lower pH]

    “pH decrease of 0.11 corresponds to approximately a 30% increase in acidity, which is an exact change in acidity (H+ concentration) of 28.8% when calculated in this way.” [explain this 30% applies to H+ ions, not pH, but still justify ‘legitimate but totally misleading to the layman’ use of the term ‘30% more acidic’]

    “Just as we describe an increase in temperature from -40°F to -20°F as warming, even though neither the starting nor the ending temperature is “warm,” the term “acidification” describes a direction of change (i.e. increase) in the level of acidity in the global oceans,” [=justifying the ‘ ‘legitimate but totally misleading to the layman’ term ‘acidification’ for a pH change from 8.2 to 8.1]

      • Hi jimbo, – Blood pH is different than human tissue pH. When we go to sleep at night our connective tissue stores by products of metabolism which are generally low pH. At sun-up on an empty stomach a lot of our body tissue cell’s pH is down somewhere below 7; so your less than or equal to 6.8 pH would be valid.

        At that pH (yes, below blood pH; incidentally arterial vs. venous blood pH’s differ as well & each moves in it’s own range of pH) our morning hormones activate. There is a bi-phasic reaction from the movement of protons (H+ ions) whereby a short term action of the hormones leads to a cascade of gene expressions (turn on some & off some). This can be up-regulation of neurotransmitters & enzymes (for example, the up-regulation of the enzyme hyaluronidase sets loose the “acidic” by products of metabolism in connective tissue & aging people might ache more upon arising).

        Urine pH & saliva pH are confounded by the proteins in those solutions; so they usually have a lower pH than the blood anyway. Morning urine’s pH is normally lower in the morning due to the the clearing of “acid” metabolites from connective tissue & by the close of day the urine’s pH has usually risen due to all the food
        derived electrolytes that will buffer the urine. Of course those with medical conditions confound those measurements of pH.

        Old people are often needing to urinate frequently at night & this depletes their electrolytes; so when parsing their pH (organ/connective tissue/blood) should bear this in mind. They often get up very early & the surge in “wake-up” neurotransmitter levels from their tissue cells’ lower than normal (young) tissue pH is a downstream result of induced proton movement.

        Teens can sleep under a CO2 monitor & not wake up; I suspect their tissue cells’ pH is less than 7 but higher than in the elderly (arterial & venous blood pH likely in standard ranges). Their growth consolidation uses so much of food’s nutrients (metabolic organs work better/efficient than when old) they stash fewer acid metabolites in their connective tissue & they’ve enough electrolytes that they don’t ache when wake up (or so I remember from long ago). Of course malnutrition would alter things like electrolytes.

        Babies urinate frequently in part because they are metabolizing rapidly & thus generating acid byproducts of metabolism. Babies’ sleep is not linked to day/night (& young children fall asleep daytime too) so they experience multiple incidents of bi-phasic proton cascades. They usually wake up crying (neurotrasmisssion) when wet themselves as cleared their acid metabolites & then they are “goo-goo-gooing” (hormones activated by acid pH have prompted growth) for about 4 hours before ready to eat again. I expect their tissue cells’ (not blood) actually use wider swings in tissue cells’ pH (they’ve not enough cellular mass to spread the acid residues of metabolism, nor muscle connective tissue mass to stash that in) & this is precisely why their growth rate is so high – the protons (H+, a.k.a. acid ion) are triggering all kinds of hormonal phase shifts.

        As for citrus pH being acidic my take is that the citric acid has the type of synergistic effect on tissue cell pH (irregardless of blood pH); it stimulates protons inside tissue cells than lead to changes in gene expression.
        It’s anti-oxidant & systemic effects are another subject.

        As for “alkaline” water all I can say is that I measured one product’s pH, then held some in my mouth & let it pour back out. The pH changed downward to close (specific data long lost) to neutral pH.

  36. As a conclusion then, it appears that the ocean “neutralization” claims of the scientists are probably close to correct.

    The trends identified by Willis (-0.019 to -0.03 pH units per decade from 1970) indicate the ocean pH has changed from something like 8.27 pH unit in the pre-industrial to something like 8.2 units in 1970 to something like 8.1 pH units today (CO2 from 280 ppm to 325 ppm to 399 ppm today).

    In the ice ages, the ocean pH might have been as high as 8.47 pH units (although noone seems to think that).

    When we get to 710 ppm CO2 in the year 2100 or 2020, the ocean pH will have changed to something like 7.6 to 7.7 pH units.

    This is all calculated with a linear formula (while it might be exponential or logarithmic or something else although I can’t seem to find one).

    • Logically the affect would likely be decreasing, as the greater the difference in PH between ocean depths due to surface neutralization, the greater the buffering affect would be as the ocean waters overturn, injecting more alkaline waters. Once again negative feedback is more likely, and the purported harms are ever more unlikely is observational evidence is examined.

    • Bill, your pH calculation makes the same mistake that AR4 made. Because of ocean buffering, the neutralization process is highly nonlinear. For 710 ppm CO2, the ‘correct’ decline in pH would be about 0.18, not 0.4. AR5 made this correction, but buried it obscurely and then went off anyway on negative coral and oyster impacts based on papers including from Feely at PMEL which are so bad they constitute academic misconduct. You can look up the details in essay Shell Games in Blowing Smoke.

  37. Excellent article with lots of good comments as well: A couple of quibbles

    I agree with at least one other person that the color choice for plotting pH seems backwards. Not sure why. Maybe indicator strips have blue at the high pH end and red at low? Can’t remember. Probably not your choice of color anyway

    I think probably Hawaii’s high pH is a symptom of lack of nutrients, and that that lack rather than high pH is the cause of the poor productivity compared to Alaska.

    FWIW California’s Mono Lake has a thriving if somewhat unusual ecosystem despite a pH around 10. Mostly algae and aquatic arthropods. But abundant enough for a lot of migrating birds to stop off and feed on their way through. OTOH, I believe that it has no native fish.

  38. Hey Willis…

    Got a citation for the following assertion?

    “despite that, the marine environment in Alaska is much, much richer in life than the Hawaiian marine environment.”

    • That question was answered in the comment right above yours. Posted an hour and a half earlier.

      It’s also something most of us learned in grade school. Cold Polar waters teem with life and diversity.

      • Sock rats has not come here to make up for his lack of understanding. Sock rat has come to cut and paste from Hot Whopper/Topic, SKS, and wherever.
        Sock rats: if you wish to wring your poor hands over CO2, you will need to find another reason besides “acidification” (gasp!) of the oceans.

    • Well if you believe NOAA Alaska’s total catch(commercial and recreational) as of 2013 was 5.2billion lbs to Hawaii’s 29million lbs. It’s not even close.

      • Willis replies to ‘socrates’:

        …you’ve provided … well, just your big mouth.

        That comment could apply to just about every D. Socrates comment. Some of them have a few factiods, but most are just annoying.

        The alarmist contingent cannot explain anything, because most of their beliefs are based on misinformation. I’ve suggested to Mr Socrates that reading the WUWT archives, keyword “CO2” for a few months, would help him get up to speed.

        But as usual he doesn’t listen to good advice.

    • Well, I was gonna reply to David but folks beat me to it. Me, I based that claim solely upon having fished extensively in both places … it’s one of my longcomings, for a lot of these questions I’ve been there and done that.

      The obvious difference is in the color of the water, with Hawaii having blue, clear water, and Alaska having green, opaque water. This is because the Alaskan waters are full of phytoplankton, the tiny green critters that are the base for all oceanic life. They are a rich green soup that supports and sustains everything from zooplankton all the way up the food chain to whales.

      The blue oceanic waters, on the other hand, are a desert as far as life is concerned. This is because the upwelling coastal waters around Alaska are full of nutrients, while the Hawaiian waters are nutrient poor.

      Alternatively, as Gonzo said,

      Well if you believe NOAA Alaska’s total catch(commercial and recreational) as of 2013 was 5.2billion lbs to Hawaii’s 29million lbs. It’s not even close.

      All the best,

      w.

      • Data on commercial fishing bears little relationship to being “richer in life”.
        For example, Kansas grows a lot more human food than tropical Amazon, but the Amazon has is much “richer in life” than Kansas.

        Secondly, fishing in both place doesn’t really pass peer review. Again, can you provide some kind of citation that backs up your claim to coastal Alaska being “richer in life” How about a count of fish species in both areas?

      • Sock rat:
        Where have you been?
        Citation?
        Okay, try a primer in oceanography. It will educate you on why upwelling produces such an abundance of marine life.

      • David Socrates January 3, 2015 at 4:08

        Data on commercial fishing bears little relationship to being “richer in life”.
        For example, Kansas grows a lot more human food than tropical Amazon, but the Amazon has is much “richer in life” than Kansas.

        Kansas grows very little food. Humans grow a lot of food in Kansas. Humans grow little food in the ocean. Since you don’t understand the difference, I fear I can’t help you with that pathetic attempt at equivalence.

        Secondly, fishing in both place doesn’t really pass peer review.

        Why on earth not? If there were great masses of fish in Hawaii, as there assuredly are in Alaska, don’t you think somebody would be catching them?

        Again, can you provide some kind of citation that backs up your claim to coastal Alaska being “richer in life” How about a count of fish species in both areas?

        No thanks. Nothing that I could do would possibly pass your faux “peer review”. Trying to please you is a fool’s errand, and while I have plenty of faults … being a fool is not among them.

        So I’ll leave it as an exercise for the student.

        w.

      • Humans harvest a lot of food in Kansas, and humans harvest a lot of food from the oceans. The equivalence is quite sound, and the analogy stands.

        “Why on earth not?”

        For the same reason that a person that claims to have been abducted by aliens doesn’t pass peer review.

        “No thanks. Nothing that I could do would possibly pass your faux “peer review”. ”

        Classic deflection. In other words, you can’t back up your claims with any reviewable data. I see.two possibilities. One is you don’t have any data, the second is you know what the data shows.

      • David Socrates January 3, 2015 at 6:00 pm

        Classic deflection. In other words, you can’t back up your claims with any reviewable data. I see.two possibilities. One is you don’t have any data, the second is you know what the data shows.

        David, believe what you want. In fact, in response to your question someone has already posted reviewable fishing data from both areas to back up my claim … and you’ve provided … well, just your big mouth. No data at all.

        And as someone remarked, any introduction to marine biology explains why the blue open ocean is a much less productive ecosystem than the green northern seas. If you don’t care to read them, that’s your business.

        And regarding your return to the Kansas example, as I said, if you can’t tell the difference between humans growing food and humans harvesting naturally grown food, you’re beyond my poor powers to add or detract from your willful ignorance.

        So no, I’m not going on a snipe hunt just so you can say something like ‘sorry, your “reviewable data” is not good enough’, just as you’ve done with the perfectly valid fish landing data … if you truly believed your nonsense, YOU would have been able to provide a host of data backing up your ridiculous claim.

        But what the heck. Let me take one last stab at it. As I’ve said elsewhere, I write for the lurkers, even if you can’t follow the bouncing ball.

        I’ve worked as a commercial fisherman a good deal in my life, and I’ve fished extensively, both in the opaque green waters of the coasts, and the clear blue water of the open ocean.

        In the ocean, what sustains and supports a mid-water full of a complex variety of oceanic life is the green “grass” of the ocean, the phytoplankton. Almost alone among the various forms of life, the phytoplankton are able to convert sunlight to edible food. Almost all of the rest of the oceanic life, from zooplankton through fish and up to the apex predators like killer whales and big sharks, depends either directly or indirectly on the phytoplankton. They form the base of the entire mid-water oceanic food chain.

        So when you see green water like you find in Alaska, you can be sure that there are copepods and anchovies and squids and fish and all the other creatures that inhabit the mid-water ecosystem.

        And when you see the clear blue waters of Hawaii, you can be sure that without the phytoplankton, the amount of mid-water life will be very small compared to the life in the green water.

        It’s just like on land. Where you see lots of grass and plants, you get lots of life … and where you see bare desert earth stretching for miles, you get much less life. It’s bozo simple biology, David—plants are at the bottom of the food chain, both on the land and in the ocean.

        Now, every fisherman who has fished both types of water knows this. And the fish landing data posted above supports this. Satellites can measure the amount of ocean life from space by analyzing the wavelengths of the chlorophyll in the phytoplankton. And the introductory marine biology texts that I’ve seen all discuss this at some length. In fact, just about everyone with a clue about the ocean knows this …

        … and then there’s you.

        So since it’s obvious that you won’t believe me, go and google it. Start with something like “blue water desert marine life”, you’ll find hundreds of references to the question, all of which agree with me. Here’s one (emphasis mine):

        The average ocean productivity is about 50 grams carbon per square meter per year. The productivity of the open ocean (ocean away from coasts) is comparable to desert production. This means that most of the ocean, or about 90%, is essentially desert. And since the ocean makes up over 70% of the earth’s surface, it is not too surprising that land is much more productive than ocean, even though life on land would seem to be tougher land plants aren’t bathed in water. Average land productivity is 160 grams carbon per square meter per year. The problem in the ocean is that the water is so deep that nutrients quickly fall below the reach of the algae and it is very difficult to get them back up. In most cases it simply doesn’t happen. In upwelling areas along coasts where the nutrients are brought back up, productivity is 5-6 times that of the open ocean and greater than the land average. It is not as high as rainforests or estuaries/salt marshes though.

        Like I said, most everyone knows this … except for you, it seems.

        w.

      • Sock rats:
        Why does it not show “major upwelling”? Because you are a would-be scientist with no faculty of judgement.

      • By the way, sock rats,
        Alaska Gyre, Alaska Current, Aleutian Current.
        Junk science is bad for the brain.

      • Here you go Mr Eschenbach….
        .
        As an “expert” fisherman, I think this paper will be enlightening for you…
        ..
        ” Our findings suggest that the contribution of species diversity to a range of ecosystem functions varies over large scales, and imply that in tropical regions, which have higher numbers of species, each species contributes proportionally less to community-level ecological processes on average than species in temperate regions.”

        http://www.nature.com/nature/journal/v501/n7468/full/nature12529.html?WT.ec_id=NATURE-20130926

        In other words…..if you want to fish somewhere “richer in life”…..the tropics is where you want to be.
        ..

      • David Socrates January 5, 2015 at 7:04 pm Edit

        Here you go Mr Eschenbach….
        .
        As an “expert” fisherman, I think this paper will be enlightening for you…

        Since I have never to my knowledge claimed to be an “expert” fisherman, your attempt to put words into my mouth is nasty and underhanded. I ask people to QUOTE MY EXACT WORDS to protect myself from people’s misinterpretations. However, you’ve taken it another and uglier step. Instead of simply not quoting me, you’ve made up a quote out of your sick imagination and have tried to use it to impugn my character.

        Not a good start, David …

        ” Our findings suggest that the contribution of species diversity to a range of ecosystem functions varies over large scales, and imply that in tropical regions, which have higher numbers of species, each species contributes proportionally less to community-level ecological processes on average than species in temperate regions.”

        http://www.nature.com/nature/journal/v501/n7468/full/nature12529.html?WT.ec_id=NATURE-20130926

        In other words…..if you want to fish somewhere “richer in life”…..the tropics is where you want to be.

        As to the diversity discussed in your link, that is the diversity of tropical reefs, which are only a tiny part of the tropical ocean, and not the part under discussion. We were talking, if you recall, about the green waters around Alaska and the blue waters around Hawaii. You know, the waters we were discussing that were shown in Figure 1. I’m more than aware of the awesome color and diversity on the reefs themselves, having spent hundreds of hours diving on them, both scuba and snorkel, both day and night, and surfing over the top of them … complete with occasionally getting pieces of the reef embedded in me when I didn’t make the wave … but then we weren’t discussing the reefs.

        Finally, you’re unsuccessfully trying to move the goalposts. We were talking about ecosystem productivity, not about species diversity.

        In other words, in addition to unsuccessfully and unpleasantly trying to stuff words into my mouth, you’ve gone off on your own tangent which has nothing to do with my original statement.

        Thanks, but no thanks …

        w.

      • OK Mr “expert” fisherman….you want direct quotes…..here ya go…

        “I’ve worked as a commercial fisherman a good deal in my life, and I’ve fished extensively, both in the opaque green waters of the coasts, and the clear blue water of the open ocean. “

      • Mr Expert Fisherman

        You demand direct quotes???
        Here is an “appeal to my own authority”

        “I’ve worked as a commercial fisherman a good deal in my life, and I’ve fished extensively, both in the opaque green waters of the coasts, and the clear blue water of the open ocean. “

      • PS….

        You post ” We were talking about ecosystem productivity”

        Great….
        ….
        But you didn’t acknowledge how “productive” Kansas is.

      • David Socrates January 7, 2015 at 2:44 pm

        Mr Expert Fisherman

        You demand direct quotes???
        Here is an “appeal to my own authority”

        An “appeal to my own authority”? You unpleasant little man, I never said that either. Once again, that’s all you.

        Do you understand what the quotation marks are for? They indicate that you are quoting someone’s exact words … except in your case, where they indicate some fantasy statement of yours that you’d like to convince folks that I said.

        I ask you to quote my words, and once again you invent some bogus quote I never said.

        Pathetic.

        In addition, I never claimed to be an “expert fisherman” in any sense. What I said was:

        “I’ve worked as a commercial fisherman a good deal in my life, and I’ve fished extensively, both in the opaque green waters of the coasts, and the clear blue water of the open ocean. “

        Show us where in there I claimed to be an “expert”. You have anointed me an expert. I never did.

        You go on to say:

        David Socrates January 7, 2015 at 2:46 pm Edit

        PS….

        You post ” We were talking about ecosystem productivity”


        Great….
        ….
        But you didn’t acknowledge how “productive” Kansas is.

        Since the discussion was about OCEANIC pH with respect to productivity, specifically the difference between the clear blue slightly more alkaline waters surrounding Hawaii versus the opaque green slightly less alkaline waters around Alaska, I fear that the productivity of Kansas is immaterial.

        If you want to write about the pH of Kansas that’s your business. I’m under no obligation to follow in your footsteps, particularly since it has nothing to do with the subject of this post

        w.

      • ““I’ve worked as a commercial fisherman a good deal in my life, and I’ve fished extensively, both in the opaque green waters of the coasts, and the clear blue water of the open ocean. “

        Your post buddy

      • “Kansas grows very little food”

        “We were talking about ecosystem ”

        Make up your mind.

  39. Excellent post, Willis. Thanks.
    The ‘acidification’ scare is mostly to the biome, which as Jim Steele points out is complex and non- unitary. And as Michal Hart pointed out, most of the harm arguments (e.g. hindered calcification) dont pass high school level chemistry and biology muster .
    Which is why when the Seattle Times published Sea Change (reporting on disastrous acidification impacts on corals and oyster spat) it took some digging into the cited peer reviewed papers to find the unbelievable deceptions at their cores. It amounts to scientific fraud and academic misconduct. Rxposed in essay Shell Games in Blowing Smoke. The oyster portion (knowing deception from NOAA PMEL still promulgated on their website despite complaint letters) was guest posted at Climate Etc. under the same title.

  40. “This is all calculated with a linear formula (while it might be exponential or logarithmic or something else although I can’t seem to find one).”

    All the calculations relating pH to CO2, temperature, depth and alkalinity for seawater can be made with CO2Sys

    http://cdiac.ornl.gov/ftp/co2sys/

    I’m moderately familiar with the excel Version

  41. Willis I may well have missed it but did you note that the pH scale is logarithmic so small changes in pH values represent quite a considerable change in H+ concentration?

    • Thanks, Ian. While that is true, the scale is logarithmic for a reason … and the reason is that it takes “quite a considerable change in H+ concentration” to change the effect of the substance in the real world.

      w.

  42. What an excellent article. Hard data and beautiful graphs in an easy to understand format. Thanks Willis.

  43. I just want to express an alternative view here. What we do know is that no one can say for sure whether a decrease of the average Ph of seawater will be a problem or not.

    We can do some assumptions based on the Ph variations on life in general, look at different districts and in different geological periods, but this cannot give a proof of whether a decrease by let us say Ph 0.3 will have only negligible effects or horrible effects.

    Some indicators of a change of 0.3 are quite disturbing; if your blood Ph, which is normally between 7.35 and 7.45, should drop to 7.1 you could fall in coma or die.
    Just as an example.

    To a more relevant example from seawater:
    The geological records show, according to the Smithsonian, http://ocean.si.edu/ocean-acidification, that there are 35 million years since we had CO2 levels as high as they are today, and nothing bad happened then. However, when the temperature and CO2 level rose quickly 55.8 million years ago, much of the shelled sea life disappeared. We can see this because the sediment changed from primarily white calcium carbonate “chalk” to red-brown mud.

    But no one can say for sure that anything of this will happen now
    So since no severe effect can be proved, there is no reason to do anything to prevent a decrease in the seawater Ph to happen or what?

    And the reason for the richer sea life around Alaska is that cold water contains more oxygen, it has nothing to do with Ph.

    /Jan

    • Jan Kjetil Andersen January 3, 2015 at 10:40 am

      And the reason for the richer sea life around Alaska is that cold water contains more oxygen, it has nothing to do with Ph.

      Dear heavens, I answered this objection yesterday … do try to keep up.

      w.

  44. Willis

    There is a lot of conjecture in this article. The generalisation that “acidity is better than alkalinity” for example. Near neutrality – which the oceans are – is best for most life. The affect of weak acid/alkaline depends on what part of the body you’re talking about (e.g. teeth vs skin). So if you have calcareous exoskeleton then slightly alkaline conditions are better than slightly acidic ones.

    The choice of acid is also important sulphuric acid is a strong acid (high – almost complete – dissociation) but tends to form CaSO4 coatings when reacting with Ca based compounds. This barrier arrests the reaction.

    In terms of oceans, the bicarbonate buffering system would suggest that, were this is the only buffering mechanism, calcareous shell thickness/growth would indeed be affected by a lowering of pH. But the whole thing is complicated by further buffering systems. In rich ecosystems with high levels of biological activity, organic acids (produced during deification, decay etc.) add to the “buffering mix” (most are weak acids with typically larger pKa – acid dissociation constant) and then there are all the other weak inorganic acids such as silicic acid. How these and the various cocktails of conjugate bases and salt parings interact, makes things far too complicated to make simple theories about how biology will adapt to what are very modest changes in pH, never mind what the affect of increasing atmospheric CO2. Furthermore, would this be a problem in a warmer ocean which would lead to degassing anyway.

    On top of all this one must add the acidifying influence of rain and fresh water, which can due to buoyancy, can affect surface, oceanic pH 100s of miles out to sea.

    • cd January 3, 2015 at 11:21 am

      Willis

      There is a lot of conjecture in this article. The generalisation that “acidity is better than alkalinity” for example.

      Since you are the only person in this thread to say that “acidity is better than alkalinity”, I fear that you are merely erecting a straw man in order to destroy it … not impressed, sorry.

      Also, putting words in quotes when nobody has said them is deceptive and underhanded … some people will indeed be fooled by that into thinking you are responding to an actual quote, rather than responding to your own imagination.

      w.

      • Willis

        This underscores a simple fact—alkalinity is hard on living creatures, much harder than acidity

        Is this not consistent with:

        The generalisation that “acidity is better than alkalinity” for example

        Perhaps I should’ve have made it clear when using the quotations as I was paraphrasing. Although if the summary statement is consistent with the original meaning then there seems little need to make the type of accusations you have.

        putting words in quotes when nobody has said them is deceptive and underhanded

        Oh Jeez, take a chill pill and get a sense of propriety – it’s a blog for God’s sake.

        some people will indeed be fooled by that into thinking you are responding to an actual quote, rather than responding to your own imagination

        I don’t. You’ll find most reports use paraphrasing and are free from litigation because the sentiment is wholly accurate. I take all inline – whether correctly or incorrectly – quotations as paraphrasing.

      • cd January 3, 2015 at 1:14 pm

        putting words in quotes when nobody has said them is deceptive and underhanded

        Oh Jeez, take a chill pill and get a sense of propriety – it’s a blog for God’s sake.

        I don’t let anyone put words in my mouth, whether it’s in a blog or a scientific paper. Quotes mean that you are QUOTING SOMEONE, and since I’m the someone who wrote the head post, you are claiming I said something that I never said. That is deceptive and underhanded. Perhaps your friends put up with it, but I won’t let anyone pull that trick on me. I’ve been misrepresented far too much to allow that kind of nonsense.

        In addition, as I said above,

        AS USUAL: If you disagree with someone, please QUOTE THE EXACT WORDS THAT YOU OBJECT TO. Even with threading, it’s often quite difficult to determine what someone’s objection might be. Quoting their own words makes it clear just where your disagreement lies.

        As a result, I (foolishly) assumed that you were quoting someone, and giving us the exact words that you objected to … but instead, you were just erecting a straw man by pretending to quote someone. Sorry, not buying.

        w.

      • And to your specific point, cd, you said:

        Willis

        This underscores a simple fact—alkalinity is hard on living creatures, much harder than acidity

        Is this not consistent with:

        The generalisation that “acidity is better than alkalinity” for example

        No, one is not “consistent” with the other, at least on my planet. I pick my words very carefully. I wouldn’t ever say that “acidity is better than alkalinity”, for example, because it’s too vague. I was specifically talking about the effects on living tissue, not whether one was “better” than the other in general.

        More to the point, I’m not interested in your attack on something that you speculate is “consistent” with what I’ve written. Your “generalization” is specifically what I’m trying to avoid. THAT’S WHY I ASK PEOPLE TO QUOTE THE EXACT WORDS YOU DISAGREE WITH! I can defend my own words. I can’t defend your curious “generalization” of my words.

        Why is this simple, polite request to quote my exact words so onerous that you feel the need to pretend to comply with it by quoting words that I never said?

        w.

      • it’s in a blog or a scientific paper

        I didn’t know you were published. But if I were quoting you from a paper then you’d be linked to.

        Quotes mean that you are QUOTING SOMEONE

        OK I wont do that again to you.

        As a result, I (foolishly) assumed that you were quoting someone, and giving us the exact words that you objected to … but instead, you were just erecting a straw man by pretending to quote someone. Sorry, not buying.

        No as I said I was paraphrasing you – there was no alterior motive. I wrongly used quotations but then it is an informal discussion and it was addressed to you – the comment will be up today and forgotten tomorrow. You’re probably the only one who is ever likely to read it anyway. This may come as a shock to you but I’m not sitting at home and work planning some Machiavellian scheme to undermine you – no really!

        one is not “consistent” with the other…

        Well you’re entitled to your opinion…

        at least on my planet

        Oh you were.

        I can’t defend your curious “generalization” of my words.

        Well let’s look at your exact words.

        This underscores a simple fact—alkalinity is hard on living creatures, much harder than acidity

        The FACT! Are you serious? So what evidence or what body of research is this FACT based? The ones you referenced – you didn’t reference any? So what evidence do you present to support this assertion of fact:

        For example, if you want to dissolve the victim of your latest murder spree, you’d use lye (a strong alkali) and not sulfuric acid (a strong acid).

        Did I quote you accurately? Now tell me was I wrong in my opinion of conjecture. I think it’s a fair judgement others can form their own opinion.

      • cd January 3, 2015 at 2:32 pm

        Did I quote you accurately? Now tell me was I wrong in my opinion of conjecture. I think it’s a fair judgement others can form their own opinion.

        Pass. I’ve made my points clearly, and I’m not playing that no-win game, so I’ll leave you to play with yourself.

        w.

      • Jan Kjetil Andersen January 4, 2015 at 1:55 am Edit

        Count me out, however. I’ve no time for such wonderful things.

        Cd seems to be a person with good knowledge of acidity and alkalinity effects on ecosystems and I think is a bit disappointing that you turn down a discussion with him/her.

        You see, most people will turn away and not come back if they are just met with insults. A certain way to waste the credibility this place has gained is to scare ordinary people away and be left with a group of angry men with similar minds cheering each other up and using most of their time in front of a computer.

        Jan, I have neither the time nor the interest in the issue to make it worth my while discussing it with a man who starts out by ignoring my request to QUOTE MY EXACT WORDS. Instead of quoting what I’d said, he made up fake words and pretended that I said them, and when I called him on it, he defended his actions.

        Now, if he were discussing an important issue, something central to the post, it might be worthwhile putting up with that kind of ugliness. But he’s picked a trivial issue, one that is meaningless to the question at hand, which is whether the oceanographic pH data helps us understand the gradual neutralization of the ocean. The issue is not acidic versus alkaline, it’s alkaline vs. more neutral … acidity isn’t even in the picture.

        As a result, I’m not interested in providing him with more opportunities to pursue his deceptive ways. Instead I invited both you and him to continue the discussion with folks like yourself … and I notice that to date you seem just as reluctant to discuss the issue with him as I am.

        As to whether this will “waste the credibility this place has gained”, that’s just the usual nonsense from the species of internet denizen known as a “concern troll”. How about you worry about your own credibility, which is at an all-time low because of your spirited but ludicrous defense of the IPCC as a source for “solid science”, and let me worry about my own credibility?

        In the meantime, I hope that you enjoy your discussion with cd, I know that I didn’t …

        w.

    • mpainter says:
      January 3, 2015 at 3:01 pm
      I hope that you are having fun, CD, because you sure make a poor impression.

      I disagree

      I think cd has some good points here. He /she? has said that she will not use a quotation mark again in this way so it is no reason to go over that again.
      One of the points made by cd is worth answering, the correct quote from the article:

      This underscores a simple fact—alkalinity is hard on living creatures, much harder than acidity.

      This is to my knowledge, not a fact. Cd has a good point there.

      /Jan

      • Jan Kjetil Andersen January 4, 2015 at 12:30 am

        I think cd has some good points here.

        Fine. In that case, Jan, you and cd can have what I’m sure will be a fascinating and enlightening discussion on the subject. Count me out, however. I’ve no time for such wonderful things.

        w.

      • Count me out, however. I’ve no time for such wonderful things.

        Cd seems to be a person with good knowledge of acidity and alkalinity effects on ecosystems and I think is a bit disappointing that you turn down a discussion with him/her.

        You see, most people will turn away and not come back if they are just met with insults. A certain way to waste the credibility this place has gained is to scare ordinary people away and be left with a group of angry men with similar minds cheering each other up and using most of their time in front of a computer.

        /Jan

      • Jan:
        Go back to your fellow warmers. It is becoming more and more obvious that you have no worthwhile contribution to make here.

    • Jan

      Thanks for your kind words. It’s “he” by the way ;)

      As for reasonable discussion, you get it with some posters and not with others. I’ll let you decide where Eschenbach sits.

      Jan if you wish to address any of the points I actually made, ones he seems to think are trivial I’d be delighted to have a discussion. To reiterate:

      But the whole thing is complicated by further buffering systems. In rich ecosystems with high levels of biological activity, organic acids (produced during deification, decay etc.) add to the “buffering mix” (most are weak acids with typically larger pKa – acid dissociation constant) and then there are all the other weak inorganic acids such as silicic acid. How these and the various cocktails of conjugate bases and salt parings interact, makes things far too complicated to make simple theories about how biology will adapt to what are very modest changes in pH, never mind what the affect of increasing atmospheric CO2. Furthermore, would this be a problem in a warmer ocean which would lead to degassing anyway.

      On top of all this one must add the acidifying influence of rain and fresh water, which can due to buoyancy, can affect surface, oceanic pH 100s of miles out to sea.

      There is huge body of literature on such issues but you wouldn’t think it given the above ‘article’ – e.g. do a search for marine humic acids. I can’t see how one could possibly explain trends in sea surface pH both in a temporal and spatial sense without an in-depth discussion of these areas of complexity. Even something such as seasonal dust storms need to be looked at – they provide external sources of weak organic acids.

  45. All. I have been talking to a number of Northwest scientists that are intimately involved in the ocean acidification issue. The bottom line is that they believe that a small change in pH will cause a major decline in a range of marine organisms, even if those organisms experience wide swings of pH in the natural environment. There is one paper they turn to more than any other: Bednarsek et al., 2014 (http://rspb.royalsocietypublishing.org/content/281/1785/20140123), Limacina helicina shell dissolution as an indicator of declining habitat suitability owing to ocean acidification in the California Current Ecosystem
    N. Bednaršek, R. A. Feely, J. C. P. Reum, B. Peterson, J. Menkel, S. R. Alin, B. Hales
    DOI: 10.1098/rspb.2014.0123Published 30 April 2014

    Based on a few cruises, they found that the amount of shell dissolution damage for pteropods was highly dependent on pH/aragonite levels. They are claiming BIG EFFECTS already:

    “Our estimates suggest that the incidence of severe shell dissolution has already more than doubled relative to pre-industrial conditions”

    I am an atmospheric scientist and not a marine biologist. But it seems far fetched to me that organisms living in an environment with large swings of pH and aragonite levels would experience significant impacts when there is a small change due to anthropogenic CO2 increases. And keep in mind that the upwelled waters are old waters, exposed to the atmosphere 40-50 years ago when CO2 levesl were much lower. Thus, is would seem to me that organisms in upwelled zones would be LEAST affected. Can anyone, with a marine biology background, provide more insight into this…thanks, cliff mass

    • In 2011, they used measurements to estimate the aragonite saturation state off of the northwest coast of North America. This is an area distinguished by the upwelling of ancient bottom waters

      Then they used models to estimate the aragonite saturation state in the year 1750 and 2100, and declared a disaster …

      In addition, the model that they used to simulate the aragonite saturation state in the year 1750 is in itself based on the modeled aragonite saturation state in the year 1750 …

      You’ll forgive me if I find that type of “turtles all the way down” analysis less than compelling … the paper I cited just above is much less than compelling, and using it to leverage the paper you cite doesn’t help things.

      w.

  46. Thanks willis, another fine post.
    I am struck by the idiocy of the “acidification” fears, if subtle changes in phH were dangerous to life, tidal estuaries would be deserts.

  47. Re Cliff Mass post: It makes you wonder what other variable could be changing, that effects shells in this way.

    Is it CO2 because that is the only variable checked and it appears to correlate?

    • Steve, we don’t even know if it is affecting shells or not. They only looked at the situation once, in 2011. It could be getting better or worse or not changing. We have no evidence either way. None. This is the first study of those shells, so we only have one single lonely data point.

      w.

  48. Reporting pH without giving the temperature of the measurement is unhelpful The ionic product for water increases with temperature, thus the pHs for neutral water at 20, 25, and 30 C are 7.08, 7.00, and 6.92, respectively.

    • The pH data from the transect is given at 25ºC. “Both datasets, obtained at 25°C and reported on the total hydrogen ion concentration scale (pHT = −log[H+]T)”

  49. On a semi related note. It is time to “terraform” the oceans. The official answer to over fishing seems to be to stop eating fish, but we could in fact greatly bolster fish stocks with more artificial (and real) reefs, as well as possibly with fertilizing areas that would readily support more life if nutrients werent so lacking.

    Ive been through this topic in depth before, and of course PH can cause issues, but we appear eons from causing massive shifts in short periods or greatly changing the extremes. Amazingly the research over decades hasnt truly cleared any of this up.

  50. Richard G January 3, 2015 at 2:41 pm

    Jim, thanks for your comments. I enjoy it when a biologist brings sensible insights to bear.
    I would add radiolarians, a zooplankton with an external skeleton made of silica, to your illustration of the complexity of the aquatic stew of many flavors that is our ocean. Many of these organisms migrate vertically in the water column during the diurnal cycle and no doubt expeience pH variations on a regular basis.

    Egads, how could I have overlooked the movement of the “deep scattering layer”? Many thanks.

    In the open ocean, the day-night vertical migration of millions of individuals of hundreds of species has been estimated to be the largest animal migration on earth in terms of tonnage. They often migrate from depths of 500-700 metres up to near the surface each night, and then return to the deeps during the day.

    Per Figure 1, this would mean that they are being subjected to a change in pH of up to half a pH unit in 12 hours … and we’re supposed to worry about the effect on oceanic creatures of a change of 0.02 pH units per decade?

    w.

  51. “And in any case, if we can’t end a sentence with a preposition … then what are we expected to end it with?”

    An example would be, using your sentence, “then with what are we expected to end it?”. :-) I like that way of writing as it’s more compact. I don’t mean ‘shorter’, I mean ‘more together’ if that makes any sense.

    • Hey, write the way you wish, Karim, every man to his own. If your words don’t sound good to you, they probably won’t sound good to others.

      My only problem is when people start claiming that there’s some kind of rule when there isn’t. As Winston Churchill apocryphally said when someone busted him for ending a sentence with a preposition,

      “This is pedantry up with which I will not put!”.

      w.

      • Not quite “Canadian” replies, but what the heck, I can tell you are trying.
        I also have the feeling it won’t last long :)
        All the best.

      • Thanks, U. K./S. It’s a work in progress, and the requirements for the Canadian passport are pretty stringent, but I’m chipping away at it …

        For some folks, however, I fear it’s like the old story of the guy who sells a mule, and tells the new owner, “He’ll do anything, just whisper it in his ear”.

        So … the new owner tries whispering, with absolutely no success. He goes and complains to the previous owner, and demands that the previous owner shows him how its done.

        The previous owner picks up a piece of lumber, smashes the mule over the head with it, and whispers in its ear. “I thought you said you only had to whisper to him!”, the new owner protests.

        “Yeah”, says the old owner, “but sometimes you’ve got to get his attention first!” …

        w.

  52. Reblogged this on gottadobetterthanthis and commented:

    Aside from Willis’ straightforward treatment here, there is the fact that CO2 levels have been MUCH higher in ages past, ages when coral reefs and shelled creatures of all types flourished just fine.
    There is nothing happening now that hasn’t happened before many times. Life finds a way, and most of the time it doesn’t even hurt unless there is a politician or government regulator involved.

    • Aside from Willis’ straightforward treatment here, there is the fact that CO2 levels have been MUCH higher in ages past, ages when coral reefs and shelled creatures of all types flourished just fine.

      Lonnie, you are right, the CO2 level has been higher in the past, but it is a long time ago. According to The Smithsonian institute it is 35 million years ago. http://ocean.si.edu/ocean-acidification

      Many of the species now living on this planet did not exist 35 million years ago. Man is one of them. Many of the sea creatures have also adapted to the level we have had the last millions of years and no one knows for sure how they will react to a sudden increase in the CO2 and a sudden drop in the Ph level.

      The geological records show that this planet experienced a sudden increase in temperatures and CO2 level 55.8 million years ago. We don’t know the cause of this, but we do know that it had devastating effects then because we can see that much of the shelled sea life disappeared and the sediment changed from primarily white calcium carbonate “chalk” to red-brown mud.

      /Jan

      • Jan, I gotta admit, I find your point of view puzzling. You appear to believe that if something is in the universe of possibilities, regardless of the odds of it happening it is worth worrying about.

        Case in point. Out of the entire history of the earth, something happened once 55 million years ago. We don’t know why, but it appears that a huge amount of methane was released into the sea, poisoning the oceanic ecosystem.

        And as a result, you are worried it might happen again. We don’t know why it happened that one time, we don’t know what the precipitating factors might have been, and as far as we know it’s only happened once in the 3.5 billion year geological history of the planet. We also know that the geological CO2 levels have been much, much higher than they are today without the same thing happening, so current CO2 levels couldn’t possibly be of concern in that regard … but despite all of that, you are worried about it, and you want to convince us that it’s worth worrying about.

        It’s not.

        You also seem to think that the projected (not real but possible) change over an entire century of 0.1 pH units is worth worrying about, describing it as a “sudden drop in the pH level” …

        Sudden drop? I’ve already shown that ocean creatures in Monterey Bay see up to three times that much change every couple weeks … and that both coral reefs and the creatures in the deep scattering layer around Hawaii see up to five times that much change in a DAY, not over a century but in a DAY. That’s a “sudden drop” in pH, Jan. What you are describing is a very gradual and small decline in pH … but you are worried about it.

        Now, as other commenters on this and other threads have made obvious, at this point most everyone knows that no matter what might be forecast, Jan will be worried about it. If it happened once in the last 3.5 billion years, Jan will be worried about it happening again. If there is the slightest change of it happening, Jan will be worried about it … heck, given your worries about CO2, for all I know you walk around with your own personal lightning rod attached to your head with a grounding strap going to your feet, because everyone knows that many more people have been killed by lightning than by CO2.

        There’s a name for that point of view, Jan. It’s called “alarmism”, and regarding the climate, people are soooo over it. We’ve heard your kind of fears and their associated doom-laden predictions over and over, and not one of them has come true. No atolls have been sunk by climate change. No Alaskan villages have disappeared from climate change. The UN’s predicted 50 million climate refugees by 2010 are nowhere to be found. Bangladesh is not underwater. The famines and mass deaths foretold by John Holdren and his pal, the dean of failed serial doomcasters, Paul Ehrlich, have not come to pass. The global surface temperature stopped warming eighteen years ago. The model predictions are now way, way off the reality. The drowning of New York which James Hansen confidently predicted is nowhere to be seen, in fact there’s been no acceleration of the rate of sea level rise predicted by so many folks of your alarmist mindset.

        So how about you give your worries a rest, Jan? We’re all aware that you are worried that everything that might possibly happen could be catastrophic, you’ve made that more than clear. So maybe you could just take that as being understood, and you focus on the science instead? You strike me as quite an intelligent man, and you’re definitely a good guy, but I gotta tell you, your constant attempt to emulate Paul Ehrlich is way past its use-by date …

        w.

  53. There was some field research covered here on WUWT a year or so ago. The article, published in JGRL is here: “Coral Reefs in Palau Surprisingly Resistant to Naturally Acidified Waters”

    http://www.whoi.edu/news-release/palau-corals

    Overlooking the constant nods to “normal” coral reef “depauperization”, the young women from Woods Hole ventured outside their NSF funding (my guess), and WAY outside the standard talking points, to find healthy, diverse coral reefs at Palau under highly carbonated (acidic) waters. They explain the mechanism of acidification, which Bio Bob and others have noted above. As ocean water sits for lengthy periods in the labyrinths of coral reefs during tidal changes, HEALTHY coral respiration adds to the CO2 saturation of the water, which lowers the pH. The result of this:

    When you move from a high pH reef to a low pH neighboring reef, there are big changes, and they are negative changes,” said Cohen, a co-author on the paper and lead principal investigaor of the project. “However, in Palau where the water is most acidic, we see the opposite. We see a coral community that is more diverse, hosts more species, and has greater coral cover than in the non-acidic sites. Palau is the exception to the places scientists have studied.”

    I couldn’t find their supplemental information, but in an e-mail their press person explained the pH levels they found in their experiments:

    From the paper’s lead author Katie Shamberger:
    pH at all our sites in Palau ranged from 7.79 to 8.12 and pH in the Rock Island bays ranged from 7.79 to 7.98 with average pH at our three Rock Island bay sites of 7.95, 7.89, and 7.84. Research into whether or not the corals in the Rock Islands are genetically adapted to acidification is ongoing so we don’t have answers about adaptation yet.

    From Willis’ Figure 5, above, I see that this is relatively low pH. If I were to hazard a guess, it would be that young, pretty scientists are finding the answers that the old, ugly ones haven’t cottoned to yet.

    Thanks for the post.

  54. Nice overview of why “ocean acidification” is nothing to worry about.

    One nitpick however is the usage of alkalinity as being the opposite of acidity. The word alkaline is the opposite of acid but the word alkalinity is not the opposite of acidity. Alkalinity is a measure of a solutions resistance to changes in pH and has absolutely nothing to do with its pH. An acidic solution can have high alkalinity even though it can’t be alkaline.

    http://water.me.vccs.edu/exam_prep/alkalinity.html

      • John West January 4, 2015 at 1:13 pm

        Arrrrg, chances was meant to be changes …. PEBCAK error.

        John, I fixed your typo … meanwhile, if not “alkalinity”, what is the opposite of “acidity”?

        w.

      • Thanks for the correction.

        That’s a good question. In general speech I’d say alkalinity is acceptable. More technically correct terms are basic and alkaline but lack the same sense for ease of use. Since all solutions are described by their pH as its “acidity” whether the solution is above or below 7 and since the same could be said for pOH, I propose the new word “hydroxity”.

        LOL.

      • Whoa. After reading that over it seems a bit cryptic. Let me try again:

        To a chemist the pH describes the hydronium ion concentration (i.e.: the acidity):

        A solution with a pH of 4 has an acidity of 0.0001 H+ mol/L.
        A solution with a pH of 7 has an acidity of 0.0000001 H+ mol/L.
        A solution with a pH of 10 has an acidity of 0.0000000001 H+ mol/L.

        Basicity or “hydroxity” would be the exact opposite for the hydroxide ion concentration on the pOH scale.

    • This is not strictly true. Both acidity and alkalinity have both common meanings and related but separate technical meanings. A solution that is alkaline has a chemical property called alkalinity which can be measured as the difference between the sum of the charge of the anions of strong acids (Cl-, and SO4– principally) subtracted from the sum of the charges of the cations (Na+, Ca++, Mg++ etc), the difference being made up in natural waters by carbonates principally, but also borates, flouride, phosphate and more. This alkalinity is commonly measured by titration with HCl. Most natural water, but not all, has positive alkalinity

      There is an analogous term acidity or mineral acidity, where the sum of the charges of anions exceeds the sum of cations, excluding H+ (charges must balance in total). This is very unlikely to occur in ocean water, but can occur in acid ground water, mine drainage or rain.

      Addition or loss of dissolved CO2 from solution does not change the alkalinity, but will change the pH.

      If you know any two of CO2 concentration, pH and alkalinity, (along with temperature, salinity and pressure) you can calculate the third.

  55. Jan, I gotta admit, I find your point of view puzzling. You appear to believe that if something is in the universe of possibilities, regardless of the odds of it happening it is worth worrying about.

    Some people behave like that Willis, but I’m not one of them as I will show below.

    Case in point. Out of the entire history of the earth, something happened once 55 million years ago. We don’t know why, but it appears that a huge amount of methane was released into the sea, poisoning the oceanic ecosystem.
    And as a result, you are worried it might happen again.

    No, that is not what I said.

    The point is that we are on the course to change the Ph level more in one or two centuries than it has changed naturally for many millions of year. The question is then whether this change may cause any harm or not.

    No one can answer that with certainty. However, we know that something similar happened 55 million years ago, and the effect was devastating then.

    Scientists don’t know why this happened, but there are several possibilities, for instance intense volcanic activity or breakdown of ocean sediments.

    I am not sitting here and worrying about whether intense volcanic activity or breakdown of ocean sediments will happen again right now. But I think it is worth being concerned about whether the anthropogenic CO2 release we see now may have some of the same effect as the sudden CO2 release 55 million years ago, because it definitely has some similarities.

    You also seem to think that the projected (not real but possible) change over an entire century of 0.1 pH units is worth worrying about, describing it as a “sudden drop in the pH level” …
    Sudden drop? I’ve already shown that ocean creatures in Monterey Bay see up to three times that much change every couple weeks

    I am talking about global averages and then a drop of 0.1 units over a century is sudden compared to millions of years. To argue that this is not sudden because the level in Monterey Bay changes more in some weeks is similar as to argue that the global temperature rise we experienced in the 1990-ies was not fast because the temperatures in my backyard changed more every day.

    your constant attempt to emulate Paul Ehrlich is way past its use-by date …

    We agree that Ehrlich was a clown Willis, and I also agree that we see far too much unfounded alarmism in the media, but I think you are wrong in labeling every concern whatsoever with regard to climate as alarmism.

    Perhaps you should worry a little less yourself. You seem to worry much about the problems associated with carbon free alternatives. I think you underestimate mankind’s ingenuity in creating good economically sound carbon free solutions.

    /Jan

    • Relax, Jan, sudden increases in temperatures have been commonplace during the Pleistocene. You wring your poor hands over one that occurred 55 million years ago.
      Well, this planet experienced a much more precipitous increase only 11,000 years ago.
      Why take fright at the PETM?

    • Perhaps you overestimate the effect of your existence.
      Would another windmill cure your anguish.
      It’s never enough is it ?

  56. All the man-made CO2 that went to the oceans since 1750 is not enough to decrease the pH of seawater by 0.1
    Even if you mix it with only the top 500 m layer. This should be easy to calculate by college level chemistry students. Yet we still hear this ‘ocean acidification’ nonsense. If true, it has a natural cause

  57. Jan Kjetil Andersen as you seem inordinately worried by changes in pH (note I use the word “seem” as it is my interpretation of what you have written and may not in fact accurately represent your thinking on this) I have included the following paragraphs from a study of oceanic pH reported by the Scripps Institute of Oceanography (https://scripps.ucsd.edu/news/1875. The paper, “High-Frequency Dynamics of Ocean pH: A Multi-Ecosystem Comparison,” was published in 2011 in PLoS One. I hope reading this lessens some of your concerns. The publication on the Scripps page is headed:

    Comprehensive Study Makes Key Findings of Ocean pH Variations; Some organisms already experiencing ocean acidification levels not predicted to be reached until 2100

    and summarises key points of the PLoS One paper. I’ve only included a small part of what is written but you may well like to read the rest.
    The researchers “found that in some places, such as Antarctica and the Line Islands of the south Pacific, the range of pH variance is much more limited than in areas of the California coast subject to large vertical movements of water known as upwellings. In some of their study areas, they found that the decrease in seawater pH being caused by greenhouse gas emissions is still within the bounds of natural pH fluctuation. Some areas already experience daily acidity levels that scientists had expected would only be reached at the end of the 21st Century”.

    “This study is important for identifying the complexity of the ocean acidification problem around the globe,” said Scripps marine biologist Jennifer Smith. “Our data show such huge variability in seawater pH both within and across marine ecosystems making global predictions of the impacts of ocean acidification a big challenge. Some ecosystems such as coral reefs experience a daily range in pH that exceeds the predicted decrease in pH over the next century. While these data suggest that marine organisms may be more adapted to fluctuations in pH than previously thought much more research is needed to determine how individual species will respond over time. Importantly, these new sensors allow us continuously and autonomously monitor pH from remote parts of the world and thus provide us with important baselines from which we can monitor future changes caused by ocean acidification.”

    Because many in the marine chemistry community have expressed concerns that ocean acidification could happen too rapidly for some organisms to adapt, the researchers said that this finding is an important step toward identifying the mechanisms some marine organisms have developed in order to cope. They also said that knowledge of actual pH ranges in various ecosystems should improve assumptions about future pH levels that can only rely on broad generalizations about seawater chemistry. Furthermore it could guide future lab and field studies that investigate the limits of resistance and resilience in various marine communities.

    • Thank you for showing me this interesting study Ian.

      I think uninterrupted growth in CO2 emissions as we see today will cause problems sooner or later, but I am not seeing myself as “inordinately worried by changes in pH”. The reason for that is first and foremost that I think mankind will gradually change to carbon free, or at least less carbon intensive, alternatives before the worst consequences of the CO2 emissions will occur.

      /Jan

  58. Thank you Mr Eschenbach, I appreciate your comments, good humour and insight.

    If I could please trouble you on a few questions.

    Is the historical pH data set in either its raw, filtered or homogenized form good enough to be used to determine ocean acidity trends?

    When the measuring instruments and methods “changed” during the 80’s, was it acknowledged THEN, that the 2 data sets could not be tied together?

    Regards

  59. I hope someone (with knowledge) is still active on this thread. I have had a problem with the concept for a long time now. I have known for some time carbonic liquids expell less CO2 when colder than warmer. Looking at this data, without questioning homogenizations issues already discussed, clearly in Hawaii the oceans are more alkaline than Alaska. Without putting SST/ OHC data side by side, I think we can all agree that the oceans are cooler around Alaska as compared to Hawaii, by personal observation I can attest to that. Putting this all together, knowing that CO2 is ‘well mixed’ within the atmosphere, we can assume there is equal CO2 available to enter the oceans in both locations. So if the oceans are less alkaline in cooler waters, then this begs the question….

    If the oceans are warming and raw data certainly questions how fast they really are warming. How can the oceans be changing towards a more acidic pH?

    Here are my further assumptions and I hope I can properly explain them.

    1. The relationship between atmospheric CO2 levels and oceanic CO2 levels is a long term complex relationship.
    2. Prior to the Industrial revolution, the oceans would have taken in the ‘maximum’ dissolved CO2 chemically possible, the oceans did not have a crystal ball in which they planned on extra CO2 in the coming centuries and left ‘extra space’.
    3. If the oceans have generally increased in energy/ temp in the past decades. No matter how much CO2 is added, the oceans would be expelling CO2 that can no longer be disolved… In the same manner an ‘ice cold’ coke removed from a cooler on the 4th of July, expells CO2, to give you the ‘sqssshhht’ sound when you pop the top, if left in the sun.

    So I am asking for constructive comments on where my assumptions are flawed, thanks.

    Brian Meteorolgy Student

    • Brian

      Imagine three scenarios. The start position is equilibrium between ocean and the atmosphere, and then we look at these scenarios:

      1. The ocean has unchanged temperature but we add some anthropogenic CO2 to the atmosphere.
      Result: Some of the extra CO2 goes down into the ocean until a new equilibrium between ocean and atmosphere is reached. We end up with increased CO2 content in both the atmosphere and the ocean.
      2. The ocean temperature increase but no anthropogenic CO2 is added to the atmosphere.
      Result: The warmer ocean will release CO2 to the atmosphere and we end up with less CO2 content in the ocean and more in the atmosphere.
      3. The ocean temperature increase and we add CO2 to the atmosphere.
      Result: It depends on how much CO2 we add and how much the ocean temperature increase.

      If we add a small amount of CO2 to the air and the ocean temperature for some reason increases many degrees, we will have a situation quite like point 2.

      However, if we add so much CO2 that the level increases 40% and the ocean temperature only increase about 1 degree Celsius, the situation will be quite like point 1. This is what we see now.
      /Jan

      • Thanks Jan, I appreciate that response, I do have one major problem with your comment. The oceans and atmosphere are not in equilibrium, they may appear to be for short periods of time. However on measurable timescales of thousands of years they are constantly changing based on the temp of the oceans. I think we can all agree that at least the past 400k years the CO2 levels have been governed by the oceans. At different Geological time periods it may have been governed by outside inputs but at least the past 400k years most likely it has been the oceans.

        Let’s put a specific date for the industrial revolution of 1850. On Jan 1, 1850 there was approx 280ppm of CO2 in the atmosphere, the oceans were holding exactly how much CO2 they could handle for that OHC and that set the level of 280ppm. Now by Jan 1, 1900 that atmospheric level had increased (don’t have time to research exactly) to let’s say 288ppm. The oceans chemically were already holding what they could hold, if they also began to increase in OHC then they should have started to expell the excess CO2 it could not hold. The oceans should be more alkaline. This is where I have my problem….

        Thanks though for those thoughts…. I need to spend some researching how CO2 or better put the mechanisms of transfer for games in the atmosphere, specifically CO2. I know certain gasses simply escape our atmosphere over time but can heavy gasses such as CO2 simply fall out of suspension in the atmosphere over time? I just can’t buy the idea that by adding more CO2 to the atmosphere you can chemically change the oceans ability to dissolve CO2…. you can put as much sugar as you like in coffee, however once you reach a certain point, no more sugar will dissolve period. In this case the sugar gets there by dumping/ gravity but does not chemically dissolve with the liquid. So I need to understand better the mechanism of how CO2 enters the oceans, is it simply mixing when the wind blows, if so once you reach saturation/ equilibrium no more will enter no matter how much extra you have. If it falls out of the atmosphere through some sort of gravity mechanism then you could add extra via seeding.

  60. I wanted to clarify my comment, I was writing on tablet that was excrutiatingly autocorrecting me, trying to get out the door for work. My problem with the concept of a warming ocean becoming more acidic simply because there is more CO2 in the atmosphere is because alarmist want/ NEED us to believe the residence time for CO2 is upwards of 300 years to in some papers 1000 years. Chemically, on Jan 1, 1850 the atmosphere and oceans were as you said in equilibrium and the oceans were holding as much CO2 as they could for that OHC. The oceans do not care how much CO2 is in the atmosphere until… they continue to cool (if that is the situation) and the atmosphere has no CO2 left for the oceans to disolve, at this point the oceans would not be at saturation, there simply would not be sufficient CO2 to attain saturation. We know this situation has not happened for (100% certainty) at least 400K years and most likely ever in the history of Earth, I am simply trying to drive home my understanding of the chemical relationship of CO2 and H2O.

    Now if we are to believe alarmist that residence time for CO2 is upwards of 300 years… The oceans SHOULD not becoming more acidic from CO2 simply falling out of suspension (not sure of the correct terminology for a gas, so I am using the term for a solid) into the oceans, we are only halfway through the residence time for the original CO2 added via industrialization.

    Finally I have read different articles/ papers on how carbonic acid forms. These seem to conflict on whether or not the CO2 has to be disloved to form carbonic acid. Which brings us full circle with the concept of mixing/ OHC/ saturation. If the oceans were saturated/ in equilibrium for that OHC on Jan 1 1850. Then simply adding CO2 to the atmosphere could not disolve more CO2, finally once the oceans begin to warm, which I truly believe they probably have to some extent. Then the oceans MUST expell CO2 that it cannot hold is solution which lowers the availability of CO2 for carbonic acid formation. Less acidic

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