The Solution To Dissolution

Guest Post by Willis Eschenbach

The British tabloid “The Guardian” has a new scare story about what is wrongly called “ocean acidification”. It opens as follows:


Pacific Ocean’s rising acidity causes Dungeness crabs’ shells to dissolve

Acidity is making shells of crab larvae more vulnerable to predators and limiting effectiveness in supporting muscle growth

 

The Pacific Ocean is becoming so acidic it is starting to dissolve the shells of a key species of crab, according to a new US study.


Sounds like the end of times, right? So let me start with a simple fact. The ocean is NOT acidic. Nor will it ever become acidic, except in a few isolated locations. It is alkaline, also called “basic”. The level of acidity/alkalinity is expressed on the “pH” scale, where neutral is 7.0, alkaline is from 7 to 14, and acidic is from 0 to 7.

Figure 1. The pH scale, running from the most acid at the bottom, through neutral in the middle, and up to the most alkaline at the top.

From the chart, the ocean has a pH of around 8 (although as we’ll see, that conceals great variation).

And from my high school chemistry class in titration, I know that adding a small amount of an acid to a basic solution, or adding a small amount of a base to an acidic solution, is called “neutralization” for a simple reason. It moves the solution toward neutral.

When carbon dioxide (CO2) dissolves in rainwater or in the ocean, it makes a weak acid. And adding that weak acid to the ocean will slightly neutralize the ocean. How much? Well, by the year 2100, if you believe the models, it is supposed to move the pH of the ocean from around 8 all the way down to around … wait for it … a pH of 7.92. In other words, a slight neutralization.

So why is it called “ocean acidification” rather than “ocean neutralization”? Sadly, because “acidification” sounds scary. We see this in the story above, where the opening line is:

The Pacific Ocean is becoming so acidic it is starting to dissolve the shells of a key species of crab, according to a new US study.” 

Well, no, that’s not true at all. The ocean is not acidic in the slightest. It is slightly less alkaline. Using “acidification” rather than “neutralization” lets us convince people that impossible things are happening. Consider the following restatement of their opening sentence.

The Pacific Ocean is becoming so neutral it is starting to dissolve the shells of a key species of crab, according to a new US study.” 

Huh? The Pacific Ocean is becoming so neutral that it’s starting to dissolve things? Say what?

Alarmism run wild.

Here’s another important and counterintuitive fact about pH. Living creatures deal with acidic substances much better than we do with alkaline substances. Look at Figure 1 above. We regularly consume quite acidic things. Grapes and orange juice are at a pH of three. Lemon juice has a pH of two, very acidic, five pH units below neutral. And at six pH units below neutral, with a pH of just one is … our own stomach acid.

But we don’t eat many things that are more alkaline than a pH of about 10, things like cabbage, broccoli, and artichoke. And while our stomachs happily tolerate a pH of one, we are badly burned by bleach, at the opposite end of the pH scale. 

Next, the required disclaimer. I have a personal stake and a personal passion regarding this subject. I live on the West Coast of the US in the very area they’re discussing, and I fished commercially in these waters for many years. So I know a few things about the local oceanic ecosystems.


With that as prologue, the new Guardian scare story is based on a scientific study called Exoskeleton dissolution with mechanoreceptor damage in larval Dungeness crab related to severity of present-day ocean acidification vertical gradients … the “ocean acidification” BS strikes again. Heck, it gets its own cute little acronym, “OA”, as in the portion of the abstract below:

Abstract

Ocean acidification (OA) along the US West Coast is intensifying faster than observed in the global ocean. This is particularly true in nearshore regions (<200m) that experience a lower buffering capacity while at the same time providing important habitats for ecologically and economically significant species. 

Now, I can’t find any reference in the study for the idea that somehow the US West Coast is acidifying faster than the global ocean. In fact, we have very little pH data for the global ocean. 

But we do have some data. One most informative graphic gives us a look at a slice of the ocean from top to bottom and from Hawaii to Alaska. Over a 15-year period, scientists traveled that route, periodically stopping and sampling the pH from the surface to the seafloor. I discussed that “transect” in my post “The Electric Oceanic Acid Test“. Here’s the ocean cross-section with its original caption.

Inset at lower left shows the area studied. Click to expand. Graphic Source

Now, there are several fascinating things about this graphic. The first is the wide range of pH in the ocean. We tend to think of it as all having about the same pH, but that’s far from true. Around Hawaii (top left of the chart), the pH is about 8.05. But at a couple of hundred metres under the surface off the coast of Alaska (top right), the ocean is at a pH of 7.25. This pH is what hysterical scientists and the Guardian would call “MUCH MORE ACIDIC!!”, but is properly called “approaching neutral”.

Next, where is the most sea life in this chart? Why, it’s off the coast of Alaska, my old fishing grounds, which is replete with plankton, herring, salmon, sharks, flounders, whales, and every kind of marine creature. They flourish in those “MUCH MORE ACIDIC”, aka “more neutral”, ocean waters.

Finally, sea life thrives at every pH in the graphic. There are fish and marine creatures of all kinds at every pH level and every area in the graphic, top to bottom and Hawaii to Alaska. They are not tied to some narrow band where they will die if the pH changes by a tenth of a pH unit over a hundred years.

So please, can we get past this idea that a slight, slow neutralization is going to kill every poor creature in the ocean? Alkalinity is a problem for sea creatures, not acidity. It’s why so many of them are covered by a coating of slime or mucus—to protect them from the alkaline seawater. Fun Fact—if you want to dissolve a fish (or a human), use lye (pH 14), not sulfuric acid (pH 1) … but I digress.

Moving on, I wrote before about the pH measurements at the intake pipe of the Monterey Bay Aquarium in a post entitled “A Neutral View of Oceanic pH“. In that post, it was obvious that the long-term trend in pH at the Monterey Bay Aquarium was smaller than the trend at the “H.O.T.” deepwater location off of Hawaii. Here’s the graph from that post showing the difference:

Figure 2. 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. You can see the higher pH around Hawaii that was visible in the previous Figure.

Sadly, the web page containing the Monterey Bay pH dataset has become some kind of unknown Japanese web-page. Fortunately, I kept the data. And I was also able to find further pH data which starts just after my old data, although it appears that the calibration of the pH sensors is slightly changed in the new set. In any case, I’ve put both datasets in one graph, with separate linear trendlines for the two datasets.

Figure 3. Twenty-five years of monthly average pH measurements at the inlet pipe that delivers 2.5 million gallons (9.5 million liters) of seawater per day to the Monterey Bay Aquarium. Two separate datasets were used. The entrance of the pipe is at a depth of 50 feet (15 metres). The size of the projected pH drop by the year 2100 using RCP6.0 is shown by the top-to-bottom size of the “whiskers” in white at the upper right.

The neutral pH of 7.0 is down at the bottom, a ways below the data. Note that the long-term trend of the average pH value of the water is about the same in both datasets, and that the trend is quite small compared to the projected slight neutralization by the year 2100.

And more to the point, that projected pH decrease by 2100 of 0.08 pH units is dwarfed by the daily change in the pH. Heck, it’s smaller than the size of the monthly change in the pH. The standard deviation of the daily change in pH is 0.6 pH units, and the standard deviation of the monthly change is 0.1 pH units.

Why is the pH changing so fast on the West Coast of the US? It all has to do with coastal upwelling. Varying winds along the coast cause deep, cold, CO2-rich, more neutral water to come to the surface in varying amounts, changing the pH literally overnight. 

Figure 4. The mechanical action of the winds blowing southward along the West Coast of the US causes the upwelling of CO2-rich more neutral water from the ocean depths. Image Source NOAA

And that constantly-changing pH is why I find these claims about oceanic creatures here on the West Coast of the US being killed off or badly injured by some trivially small slow change in pH to be totally unbelievable. Every living being in the ocean along this coast undergoes much, much larger pH changes from one day to the next than they will see over the next century.

There’s one more dataset that I have to add to this before turning to the study itself. The study actually takes place up in the area near Seattle. So what is the oceanic pH up there doing?

Turns out it is very hard to find long-term pH measurements in that area. The best that I’ve been able to find are an intermittent series of measurements from an offshore buoy on the coast of Washington near the Strait of Juan de Fuca, a lovely part of the planet that I battled through a while back. Here’s where the La Push buoy is located:

Figure 5. The yellow square shows the location of the “La Push” offshore buoy. The Strait of Juan De Fuca is the blue channel leading into the land. Seattle and Tacoma, Washington are below the inner end of the Strait. Vancouver Island, Canada, is on the north side of the Strait.

It appears that the buoy is brought in when the weather gets very rough, because there is a gap in the data each winter. Here’s the La Push buoy data, to the same scale as the Monterey data above.

Figure 6. Daily surface pH records at the La Push, Washington offshore buoy. The background is an offshore island near La Push.

Once again, we see the same situation. The pH changes are much larger than the size of the projected change between now and the year 2100. And while I wouldn’t put much weight on the trend line because of the gaps in the data, it’s quite possible that the trend is actually becoming slightly more alkaline.

How can it become more alkaline? Remember that along this coast, the swings in the pH, and the average pH itself, are not direct functions of CO2 levels. Instead, they are determined by the instantaneous and average strength of the wind. If there is more wind, more of the deeper, more neutral waters come to the surface to lower the surface pH, and vice versa. 

And lest you think that such swings in pH are limited to this coast, here’s some data from around the planet.

Figure 7. pH values and variations from different oceanic ecosystems. Horizontal black “whiskers” show the range of the pH values. The size of the expected slight neutralization by the year 2100 according to RCP6.0 is shown by the red whiskers at the top. Ischia South Zone, the site that goes the lowest in pH, is on the side of a volcano that is constantly bubbling CO2 through the water. DATA

Let me close by looking at the study itself, at least as much as I can bear. I’ll discuss a few quotes. The first line of their “Highlights” says:

Coastal habitats with the steepest [vertical] ocean acidification gradients are most detrimental for larval Dungeness crabs.

There’s no such thing as a “vertical ocean acidification gradient”. There is a vertical pH gradient, as you would expect with upwelling deeper CO2-rich water hitting the more alkaline surface waters with less CO2. But this is a natural condition that has existed forever and has nothing to do with “OA”. And they present no evidence to show that the gradient will change significantly in the future.

Next, in their conclusions they say:

Like dissolution in pteropods, larval dissolution observed in Dungeness crab is clear evidence that marine invertebrates are damaged by extended exposure to strong present-day OA-related vertical gradients in their natural environment.

However, they present no evidence that past “OA”, or mild oceanic neutralization, has had any effect on the “vertical gradients in the natural environment”. The vertical gradients in pH off of the coast are a function of the upwelling, which in turn is a function of the wind, which is constantly changing. They don’t have long-term data for the vertical pH gradient. Instead, they went on a two-month cruise, took some samples, and extrapolated heavily. We don’t even know if they’d have found the exact same “dissolution” a hundred, fifty, or twenty-five years ago. Or perhaps the dissolution was particularly bad during that particular two-month period in that particular small location. This should not surprise us. One reason that so many marine creatures spawn hundreds of thousands of larvae is that many, perhaps most, of them will drift into inhospitable conditions and die for any one of a host of reasons—problems with salinity, turbidity, pH, predators, temperature, the list is long.

Finally, this paper does prove one thing—that Neptune, the trident-wielding god of the ocean, definitely has a sense of humor. Here’s the ultimate irony. 

They couldn’t see the parts of the crab larvae that they wanted to examine because those parts are covered by the “epicuticle”, the outer layer of the hard carapace that surrounds the larva. So they first had to dissolve the epicuticle in order to get access to what they wanted to study. Here’s their description of the problem and the solution. (The “megalopa” are a stage of the larval form of the crabs).

The carapace epicuticle, which otherwise overlies the crystalline layer and makes dissolution observations impossible, was removed from each megalopa prior to analysis. This was accomplished using sodium hypochlorite, which efficiently removes the epicuticle but does not damage the crystalline layers underneath, even at high concentrations.

Care to take a guess at the pH of the 6% solution of sodium hypochlorite, which is what they used to dissolve the carapace epicuticle? 

It has a pH of 11 or more, almost at the very top of the scale in Figure 1, very strongly alkaline. 

So it no wonder that Neptune is laughing—they’re all up in arms about “acidification” dissolving the crab carapaces … but in the event, they’re using an alkaline solution to actually dissolve the crab carapaces.

Ain’t science wonderful?


It’s clear today, and from my house perched high up on a hill six miles (ten km) from the coast, I can see a small bit of the very part of the ocean that we’re discussing. It’s foggy down there and it’s clear up here, as is often the case. And right out there, millions of marine creatures are happily going about their lives as the pH gyrates up and down every hour, every day, and every month. 

If a slight oceanic neutralization were going to injure them as we are franticosolemnly assured at every opportunity by the bad boffin boys and the popular press, those oceanic inhabitants would all have died long ago.

My very best to everyone on a sunny winter day,

w.

PS: After early years of having to point out that “No, I didn’t say that, I said nothing like that”, I’ve taken to asking those who comment to quote someone’s exact words that you are going to discuss. This avoids endless misunderstandings and arguments.

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197 thoughts on “The Solution To Dissolution

  1. As a career chemist i thank you. I always found the terminology acidification very annoying. The other thing I would like to see someone take on is “warming oceans”. This assertion is based on tiny changes in average ocean temperature. The last one I saw was 0.1C since 1960. This cannot be a robust number. Error margins are never mentioned. The real result could be zero as well. Given the puny heat capacity of air vs water i don’t expect much future change

    • Mike, thanks for your kind words. Inter alia, the logical problem is that something can’t become “more acidic” as folks keep claiming, unless it is acidic to start with …

      w.

      • Exactly, Willis.

        Claiming a slight reduction in pH makes seawater “acidified” or “more acidic” is equivalent to saying that a positive real number is made “more negative” by reducing its magnitude. Nope – it is just a smaller positive number, not a “negafied” number.

      • Yep, I think the problem is the pH scale itself and not understanding what it actually means. Acids and bases are binaries with completely different properties, not degrees of the same thing.

        Furthermore, where are they getting that continental shelfs have less buffering capacity than the open ocean? It’s the opposite. The shallow marine environment is where you have the carbonate factory as well as where all of the salts from rivers runs are dumped into the marine environment. The saturation state of Aragonite and High Mg Calcite is so high in the shallow oceans that you can literally have non-biogenic precipitation of these minerals as whightings or oolites.

        • @RWT “I think the problem is”. The problem is they are mis-stating the facts and deliberately misusing words in order to push their agenda.

        • It is exactly that—degrees of the same thing. And what it means is very simple. Lower case p means “negative common logarithm of” and capital H means “hydrogen ion concentration in moles per liter.”

          Pure water self-dissociates (breaks apart) into hydrogen ions and hydroxide ions constantly. These ions also constantly come back together to form water molecules again. The equilibrium state is such that the number of dissociated molecules is really close to 0.0000001 mol/l at 20C. Log of 10^-7 is -7, so the pH of water is 7.

          Add something that provides more hydrogen ions, say hydrogen chloride (hydrochloric acid), to water, and the hydrogen ion concentration goes up—so the pH goes down. HCl is very soluble in water and breaks down nearly 100% (this is the dissociation constant, another little p for negative log, pK) into a hydrogen ion and a chloride ion. Make a solution (do as you aughta, add acid to watta) with 10 moles of HCl per liter, almost all of which dissociates, and the H+ ion concentration is 10 mol/l, whose log is 1, so the pH is _negative_ 1. They never show negative pH on those charts, do they?

          Add something like sodium hydroxide, and there will be a lot of excess hydroxide ions compared to water—which suck up most of the hydrogen ions in the water. Put one mole of NaOH per liter, and the concentration of H+ ions drops to 10^-14, a pH of 14. You could put in more lye, it’s soluble enough, and the pH would be greater than 14, something you also don’t see in the chart in the newspaper.

          It’s that simple, and a continuum of the same thing.—hydrogen ion concentration. It’s not two binaries.

    • I disagree. Willis’ tiresome arguing about semantics whenever this comes up is not only tedious, it detracts from the useful things he actually writes.

      “Acidification” is not an incorrect term. It may be used to be misleading in some instances, however it is factually correct.

      Pick your battles more wisely Willis.

      • Acidification of a basic solution is a non-sequitur and totally inappropriate and non-scientific.

        You are flat out wrong.

        • I have to defend good Dr.Torch. Isn’t “Acidification” an excellent term to scare children?

        • “Acidification of a basic solution is a non-sequitur”
          No that is a non sequitur. It doesn’t follow in chemistry or normal usage. If you add acid to something, yo“Acidification of a basic solution is a non-sequitur”
          No that is a non sequitur. It doesn’t follow in chemistry or normal usage. If you add acid to something, you acidify it. The only requirement is that what you add is more acidic than what you had.

          If you put a saucepan on the gas, you are adding heat, and so heating it. It doesn’t matter whether the saucepan contained melting ice, melting lead, or melting nitrogen.

          • Nick, I figured you show up soon to make some bogus bullshit argument why scaring people with “acidification” is the perfectly reasonable thing to do. Your claim about “chemistry” is nonsense. Read any textbook about titration and see what they call it.

            I’m not going to reply, no good wrestling with a pig, you just get dirty and the pig enjoys it. I’m just going to laugh and point at how predictable you are.

            Sorry, but in this case, you’re just reverting to being Nick “Racehorse” Stokes again. You’re worth listening to some of the time. But other times, you’ll grasp at any straw, and while it’s somewhat amusing to watch you waving your arms and screaming, it’s not worth responding to in any serious manner.

            You can reply to this if you wish. For me, you’ve canceled your vote in this discussion, I’ll do nothing but point and laugh.

            w.

          • You’re wrong throughout, Nick.

            Acidification means to make acidic. It does not mean to make less basic.

          • If you add acid to something that is alkaline to start with and is alkaline afterwards then I think that ‘neutralised’ or even ‘less alkaline’ are more honest terms than ‘acidified’ . Why would you use the term ‘acidified’ especially knowing how misconstrued it will be by the msm and misunderstood by the general public?

            The key word here is not to do with the scientific options it is ‘honest’, i.e. to do with objectivity, integrity and credibility in the ‘witness box’.

            As for heating a saucepan, saucepans do not have a scientifically defined and significant ‘balance point’ of neutral heat content or temperature analgous to reference to the chemical behaviour (acid vs alkaline) as distinct from the parameter value, pH.

            It may well be valid science to measure the ph of ocean waters and gather data on crustacean shells. It is not robust science to imply causative linkages fro the former to the latter and then to publish sexed up narratives that generate the feel of authority by introducing ‘scary’ terms like acidification. That is junk science and coat trailing by people of the make for their next grant, i.m.o.

          • I think your points are mostly persuasive. What is the parallel term for adding a base?

            It doesn’t exactly roll off the tongue, does it?

          • Nick,
            Go to AR5 Summary for PolicyMakers,
            https://www.ipcc.ch/stir/assets/uploads/2018/02/WG1AR5 SPM Final.pdf
            What does the science tell us about ocean acidification?
            “B2. Ocean,
            Fifth dot point is about ocean salinity.There is medium confidence that regional trends in ocean salinity provide indirect evidence that evaporation and precipitation over the oceans have changed ( Medium confidence, 2.5, 3.3,3.5)”
            “B5. Carbon and other Biogeochemicals Cycles.
            …The ocean has absorbed about 30% of the emitted anthropogenic carbon dioxide , causing ocean acidification (see Figure SPM4 )(2.3,3.8,5.2,6.2,6.3)
            Sixth dot point-
            “Ocean acidification is quantified by decreases in Ph.The Ph of ocean surface water has decreased by 0.1 since the beginning of the Industrial era ( high confidence), corresponding to a 26% increase in hydra ion concentration (see Figure SPM4 ).( 3.8,Box 3.2.)”
            SPM 4 has a (b) graph of surface ocean CO2 and pH.Measurements shown there are from three stations from the Atlantic and Pacific Oceans. The graph lines show the pH drifting down from 8.12 to above 8.6 pH at those sites.
            And that in a nutshell is the case for ‘ocean acidification’.
            In the latest State of the Climate Report in Australia, the various pH levels around the Continent from the Indian to Pacific Oceans are said to show an overall decrease in Ph from 8.18 to 8.08 over the last century or more, with the caveat that readings at various sites differ periodically.
            A similar result to the IPCC Report.
            Now here is Dr.Roy Spencer from ”Global Warming Skepticism for busy people “-
            “It should not come as a surprise that there is a difference between CO2 dissolved in water and hydrochloric acid.Marine life ,like vegetation on land, uses carbon from CO2 to help grow life forms. Jim Steele, director emeritus of the Sierra Nevada Field Campus, San Francisco State University has stated:
            “….all ocean acidification models are deeply flawed , based on an incorrect assumption that CO2 enters the ocean and is then transported like an inert tracer.But CO2 is not inert! When CO2 first invades sunlit surface waters ,it indeed dissolves into 3 forms of inorganic carbon (DIC) and lowers pH.But in contrast to those models, DIC is rapidly assimilated into particulate organic carbon via photosynthesis which raises pH. Particulate organic carbon ( alive or dead) is heavy , and if not recycled, it sinks. For millions of years, this process created and maintained a DIC/pH gradient with high pH/ low DIC near the surface and low pH/ higher DIC at depth”.
            Dr.Spencer concludes
            “…my understanding is that an increasing number of studies with more realistic laboratory experiments are now showing that shelled organisms actually benefit from more dissolved CO2 in the ocean.”
            Lastly see my other comment to Willis on Hoffman et al 2011.

          • “saucepans do not have a scientifically defined and significant ‘balance point’ of neutral heat content”
            Nor is there such a universal balance point of acid-base reactions. Titration was mentioned above. Titration is done to reach an equivalence point, where you have added an equivalent amount of acid to the original alkali (or vice versa). That is called the equivalence point. For strong acid and strong base, that is at pH 7. But these substances are not part of the normal bio environment. Instead there are weak acids and bases, and as Wiki will tell you, where they are involved, there is no universal equivalence point, and certainly not pH 7.

            This is the key point here. We are dealing with a buffer, and what matters is the concentrations of the buffer species. With seawater, CO₃⁻⁻/HCO₃⁻ is the buffer that matters, and its equivalence point, is about 9.13 (Zeebe). So sea water is on the acid side of that, which means CO₃⁻⁻ is depleted. This matters because of its role in the solubility equilibrium of CaCO₃, and the tendency of sea shells to dissolve. This is increased as you move further toward the acid side of the equilibrium. That is very reasonably described as acidification.

          • Nick, you are hilarious. Do you really think your oh-so-learned and absolutely true scientific points are either relevant to the real issue, which you clearly don’t even recognize, or are convincing to one living soul?

            Give it up and take up something more useful, like picking your nose. At least you’ll get something out of that.

            w.

          • So adding heat to a saucepan of cold water makes it “more boiling”?

            You do come in with some helpful comments, but to incessantly try to be the contrarian does disservice to all of your posts.

            You cannot make a basic solution more acidic becasue it means absolutely nothing to a chemist. You can only make a basic solution less basic, neutral or acidic by adding acid. Then you will be understood.

          • So I guess if you had a saucepan and you turned down the heat from 180 to 175 you would describe the contents as becoming ‘more frozen’?

          • Nick, “etc., etc., there is no universal equivalence point, and certainly not pH 7.

            This is the key point here. We are dealing with a buffer, and what matters is the concentrations of the buffer species. etc.

            Wrong throughout, Nick. Acidity and alkalinity are defined by any pH below or above, respectively, pH 7.

            Buffer pH is not defined as acidic when on the low pH side of an alkaline (pH>7) equivalence point.

      • The fact is the Alarmists are using the term Acidification as a pejorative. While you may claim it is not “an incorrect term”, it is definitely intentionally used to make people falsely believe the ocean is acidic. It is intentionally used to mislead the public.

        • Yes, I think that is the chief issue in this case.

          The alarmists intentionally use language to frighten, to evoke an emotional response. “Climate crisis, catastrophe, extinction,” etc., all without educating or explanation.

      • Nope he’s right. Most kids do titration at school. Pointing out the deceptive usage of terminology can only make them question why they are using it.

        • Acidification is most definitely used incorrectly by alarmists and anyone who speaks of ocean acidification.
          (BTW, I have a chemistry degree)
          Look at any dictionary, legal dictionary, scientific dictionary, regular old dictionary…and you will find only one definition of the word acidification: The process of making or becoming an acid.
          The ocean will never be acidic.
          It is a multiply buffered basic solution.

          And since when is asking questions while in school a bad thing?

        • Sparko,
          After reading the thread over again, I think I erred when I responded to you.
          I think you were addressing Dr. Torch, who is wrong in what he said.
          So…sorry about that.

          • This is a perfect example of why I ask people to quote the exact words you are responding to …

            w.

      • Pick your battles more wisely Willis.

        Now I disagree — this was a very wise battle.

        For example, while a few hundredths of one degree, technically, is warmer than a figure
        the same few hundredths of one degree less, is it really ethically correct to say this means that temperatures are rising catastrophically?

        I don’t think the “battle” here was really about technicality — it was about HOW technicality might be abused to fabricate greater falsehoods and needless worry.

      • “Acidification” is not the proper term in the context. Semantics have nothing to do with it. As a career environmental engr trouble shooting water and wastewater treatment issues, I have never experienced a situation where someone with the proper background used the term “more acidic” to describe a reduction in pH from an 8 to a pH of 7.92. NEVER. Other factors (i.e. alkalinity) also play a role. Mr. E is correct.

          • John,
            Burning fat makes acids called ketones and, if the process goes on for a while, they could build up in the blood. The buildup of these acids is “acidosis.” In severe cases the blood may become acidic. “Acidosis” — a buildup of more acid molecules — does not make the blood more acidic unless the pH is below 7.0.

        • Gerald,
          It would help the rest of us understand your criticism if you specified who you are addressing.
          Just sayin’.

      • No he is not. It is a fundamental mathematical relationship of the concentration hydrogen ions in a solution.

        To suggest, claim otherwise is to make you the science denier.

        • It is simpler than that…it is the very simple definition of what pH range makes something an acid.
          The scale is binary.
          Above 7, basic.
          Below 7, acidic.
          Period.
          Those are definitions, not suggestions.

        • JE Hill,
          Once again, not specifying who you are talking to makes it unclear what you are saying exactly.
          So I might have been addressing my first comment in reply to you, (when it shows up) to the wrong person.

      • I read that paper, from a Sigma Xi link, Smart Brief. Look at Futurism, hardly semantics. https://futurism.com/the-byte/ocean-getting-acidic-dissolving-crabs
        “The Ocean Is Getting so Acidic That It’s Dissolving Crabs’ Shells”

        Exoskeleton dissolution with mechanoreceptor damage in larval Dungeness crab related to severity of present-day ocean acidification vertical gradients
        https://www.sciencedirect.com/science/article/pii/S0048969720301200 Open Access

        “The carapace epicuticle, which otherwise overlies the crystalline layer and makes dissolution observations impossible, was removed from each megalopa prior to analysis. This was accomplished using sodium hypochlorite, which efficiently removes the epicuticle but does not damage the crystalline layers underneath, even at high concentrations (Bednaršek et al., 2012)……..To our knowledge this is the first time that OA-related dissolution of calcite structures in situ has been demonstrated for crustaceans…….Alternative hypothesis for explaining internal dissolution might be based on the severity of external dissolution extending much deeper (Fig. S4) to initiate the endocuticle dissolution. Once the dissolution of the external carapace dissolution is initiated, the mineralogical-elemental structure of the mid- and endocuticle can allow for more rapid progression.” No kidding?

        The paper is preaching, obscured by many citations about “acidification.”

      • Willis is correct. It is neutralization that is going on. It will not be acidification until you get under a pH of 7. The term of acidification of the ocean is the highly misused term.

      • Meh.
        It is amazing how defenders of Caldeira’s marketing brainstorm keep trying to take over the language of the discussion.

    • Error margins are never mentioned.

      Error margins are not required in climate science, ever. Evidently you never got the memo.

      However, every number published must have at least 2 numbers to the right of the decimal point and cutting edge organizations with big computers and elegant algorithms like Berkeley Earth have three (even back to the late 1700’s), which makes it even more accurate.

      http://berkeleyearth.lbl.gov/auto/Global/Raw_TAVG_complete.txt

      • Sir, your comment made me snort/laugh. These guys (climate scientists) fail everything we were taught about significant figures, propagation of error, and confidence intervals. I needed a good laugh this evening.

    • @Mike

      Never finished my degree…

      However I was thanking back to my AP Chemistry class in High school and GenChem 101 in college and how basic this chemistry is and how the use of these terms in a non-robust and non-scientifically rigorous way with willful intent is a form of malfeasance.

      • Probably most scientific calculated readings and results are justified to 2 or 3 significant figures only, but some people can’t resist using all the figures from a readout or spreadsheet. Sad, but funny too.

        Precision, aka repeatability is one thing, but reproducibility is another. Send an identical sample to 3 labs for chemical analysis using identical test procedures and rarely do they agree within a few percent. Here’s an example:

        Lab 1 – 43.33 ppm
        Lab 2 – 54.457 ppm
        Lab 3 – 48.7892 ppm

  2. Bravo, Willis.

    Credibility Means Something

    In fact, there have been so much under-informed writing and reporting about fracking it makes the cognoscenti of unconventional oil downright embarrassed. Defying intellectualism, I suppose because Fracking sounds bad and involves fossil fuel.

    I don’t “believe” in today’s environmental activism. And, I don’t believe much in the agitprop from the Major Media and Big Green Machine.

    After billions and billions of dollars spent on environmental activism, the only accomplishment is insuring nothing got built.

    • You’re welcome, Steven. The curiousity about fracking is that it was first used in 1947, the year I was born, and it has been in use for my entire lifetime. The protests against it only started when it began to be used on horizontal wells … which leads to the bizarre conclusion of:

      Vertical fracking good

      Horizontal fracking bad

      w.

      • Love your stuff Willis
        Several years ago I ran into a history article about Civil War veteran Lieutenant Colonel Edward Roberts who, shortly after the end of the war”, began increasing production in both water and oil wells by exploding either “Roberts Torpedo’s” (alias “mines”) or liquid nitroglycerine. He improved on the concept by filling the wells with water to concentrate the fracturing effect.
        As always, thanks for your well written and understandable (for a layman) articles.

      • “Vertical fracking good

        Horizontal fracking bad”

        No, fracking campaigns with relatively tiny volumes, and properly disposing of those volumes in competent haz waste wells, at acceptable injection pressures, good. Fraccing campaigns with volumes orders of magnitudes higher, in spaghetti nests of hydraulically incompetent laterals, with the contaminated aqueous slurry used over and over, and only then injected down antique, over worked haz waste wells, bad. One has acceptable levels on environmental damage (at least circa 1947), the other doesn’t

      • Willis: The MODERN era of fracturing started in 1947. This is hydraulic fracturing.

        But fracturing rock formations using explosives started in about 1850 for water wells. This technique was first applied to oil wells after the Civil War.

  3. Can’t argue about the article.
    There is however an impact on near-shore shellfish hatcheries and rearing facilities. Locally sea water needs to be treated with ash to raise the pH to a level that shellfish would thrive. We live in a wet maritime climate of 12 feet of rain a year and lots of overcast days. In one quick study found that it took only 3 or 4 hours of sunshine to raise the pH significantly in an isolated mass of water. Sunshine and algae make fast work of dissolved CO2 in the ocean.

    • Haverwilde January 31, 2020 at 10:34 am

      Can’t argue about the article.
      There is however an impact on near-shore shellfish hatcheries and rearing facilities.

      Thanks, Haverwilde? Citation? The claims about this from Washington State turned out to be totally bogus.

      w.

    • it’s upwellings not atmospheric CO2…
      …and the crabs they are talking about migrate down to lower O2..higher CO2…water to digest their food
      deeper water….less predators

    • Here is something I don’t understand about that.
      I’ve noticed that most of the commercial oysterbeds are deep inside the Sound, and at the mouth of river estuaries at that. If neutralization is so harmful, wouldn’t the deluge of freshwater every rainfall kill them off?

  4. A couple of points:

    1) we as real scientists, unlike the media and the fake wannabe scientists infesting the climate alarmist clique, must reject outright any use of the phrase “ocean acidification” as a fake term, as there is no such thing. If a given solution is basic, it cannot be acidified .. it can only be made less basic, i.e., more neutralized (it cannot be “neutralized” unless and until it has a pH of exactly 7.0.

    2) It is not even as the writer wrote, that you add an acid and the ocean becomes more neutralized. Rather, there is also the matter of buffering capacity.

    Buffering capacity: The buffer capacity is a quantity in resisting the pH change at the time of addition of an acid or base. The higher the acid concentration of the buffer then the buffer capacity will be higher as well. The buffer capacity can also be defined as the amount of mole of strong base needed to change the pH of 1 L of solution by 1 pH of unit. Buffering capacity is also analogous to “alkalinity” which is not the same as pH.

    The buffering capacity (or alkalinity)of sea water varies somewhat around the world and with depth.

    The buffering capacity of seawater is somewhat akin to a physical analogy of a mechanical damper, which tends to reduce the variation in mechanical response .. like a shock absorber on a motor vehicle.

  5. Willis, as an owner of a salt water tank in my living room ( 300l is a puddle, okay) I want to add one more thought: There are daily pH- changes depending on the photosynthesis of the corrals and plancton ect. which live there in the sunlight of the reefs. The variations are about 0.15 pH or so, deepest values in the early morning and highest values just after sunset. Therefore it makes sense to measure the pH always at the same time of the day because the wobbles are bigger than the projected pH decline to the end of the century. However, the “acidification” -story is one more issue of “overconfidence in gloom’n doom”

    • Every 24 hours, the ocean changes pH at the surface in response to change in temperature and photosynthetic activity.
      It drops at night, and goes back up in the daytime.
      Another interesting thing happens while that diurnal cycle is occurring: Every morning, a huge number of the species which inhabit the ocean descend to depth to wait out the daylight hours.
      And then at night they return to the surface to do their night time thing.
      Copepods (crustaceans), molluscs, fish…they do this every single day and night.
      What that means is, they go down where the pH is much lower during the day, and only rise to the surface when the pH drops…at night!
      IOW…they avoid being where the pH is highest.
      This phenomenon has a name…it is called the diel vertical migration.

      Not only does pH vary greatly on a diurnal cycle, it varies hugely between the various ocean basins and, as Willis ably points out, across each basin depending on latitude, depth, and temperature at the surface and of the water column.
      And it changes an even larger amount in the most productive ecosystems, such as the cold waters of the polar regions, and the places where volcanic activity is taking place…at volcanic vents and the so-called black smokers along the mid ocean ridge system… and it varies strongly to the acidic side of the scale where rivers mix with the oceans…in bays and estuary systems, because most fresh water is acidic, often highly so. And all sorts of freshwater crabs, clams, jellyfish, bony fish, and everything else…live and prosper just fine in freshwater ecosystems with a pH on the acidic side of the scale.

      Living creatures have this thing called homeostasis, and all sorts of mechanisms for maintaining it.
      Warmistas and alarmists operate on the assumption that life is tenuous and fragile, but life is not tenuous, or fragile…it is endlessly adaptable and resilient.

      Like pretty much everything claimed by alarmists, they things they claim about the oceans being negatively affected by increasing CO2 in the air is completely meritless and based on bad science, ignorance, and fundamental lack of adherence to basic principles of scientific inquiry.
      They are also in every case almost exactly wrong.

      • Oops, I said the wrong thing here:
        “…where the pH is much lower at night, and only…”

        I meant to say, they go down to depth during the day, and return to the surface at night.
        IOW, they hang out where the pH is lowest…surface at night, depth during the day.
        Not what one might expect if lower pH was dangerous and harmful.

        The corrected sentence would be:
        “…where the pH is much lower by day, and only…”

        • Fixed. I hate those kind of mistakes, and since WordPress doesn’t have a comment editor, I’m it by default.

          Next, I never thought about the diel vertical migration in terms of pH. Let’s see … the migration is typically about 500 metres vertically. And per the graphic in the head post, this involves an amazing change of half a pH unit in a couple hours!

          Half a pH unit in two hours vs a projected change of 0.08 pH units in a century?

          Yawn …

          w.

          • Exactly!
            Somehow the people who represent themselves as the science experts of the ocean never mention this sort of thing.
            In fact it seems they studiously ignore it…if they ever knew it to begin with!
            I think those crabs were happy as clams, until the people doing this paper dissolved their shells with concentrated bleach, that is.

          • Interesting to think of diel vertical migration as a chemotropic response rather than/ as well as/ a phototropic response. Hmm(scratches chin), complicated business this biosphere.
            Kudos to Willis and Nicholas M.

    • frank, if you run a calcium reactor….how low do you have to get the pH to dissolve calcium carbonate?
      …that should answer the crab question

    • “corrals and plancton ect”

      I know what corrals are, that’s where you keep the horses. But what is “plancton ect”? And why is all that stuff in your fish tank?

  6. Oceans were mildly acidic in the Late Hadean (4.2 to 4.0 Ga), when life appeared on Earth. Seawater was neutral by the end of the Archean Eon, and close to its present pH by the end of the Proterozoic.

  7. I always thought “acidification” was incorrect in describing a change in ph above 7. I am happy you have provided facts to support my opinion.

    • You saved me the trouble, since I live on said Island I find there is often confusion because Victoria the city, is on Vancouver Island whereas Vancouver, the city, is not.

      • Slap to the forehead. I once flew in to Vancouver for a “day trip” meeting and assumed I was on the Island…never referred to a map for some reason.

        Victoria…not on Victoria Island (in the far north) and Vancouver…not on Vancouver Island.

  8. Nice article! I wish people writing articles like these would spare a thought for paleo data and at least address inconsistencies with their interpretation. For example the fossil data show abundant crab species from the Eocene and Miocene, when atmospheric CO2 is interpreted to have been ~600-1000 ppm. The significantly higher atmospheric CO2 at those times does not seem to have been fatal to crab populations. https://www.sciencedirect.com/science/article/pii/S0012821X1830356X

    • Decapods evolved in the late Silurian or early Devonian Period, ie under CO2 levels of 4500 to 2200 ppm. If anything, a paltry 400 ppm is not optimum for them.

      The crablike form has evolved at least five times among decapods. Crustaceans with shells evolved in the Cambrian, ie under 7000 ppm. The top predator of that period was the crustacean Anomalocaris.

  9. Willis,

    Excellent article. I would have preferred to see some actual numbers about pH and the type of ions it defines, but that is ok.

    The real part that defies me is similar to many studies. The study doesn’t seem to have any data about laboratory testing to determine ranges of pH and their affect on the crabs. It would seem data from a carefully “controlled” group of laboratory tested subjects at various pH’s would provide a standard to judge ocean caught subjects against. As it is, they are attempting to collect info on two variables at the same time.

    • Jim Gorman January 31, 2020 at 11:27 am

      Willis,

      Excellent article. I would have preferred to see some actual numbers about pH and the type of ions it defines, but that is ok.

      Thanks, Jim. I write for an imaginary person that I call the “interested layman”. This is a woman or a man who is interested in the world around them, but has little scientific knowledge.

      One thing I know about the interested layman is that by and large they are allergic to numbers and math. My totally unscientific rule of thumb is that for every numeral I put into a post, I lose one reader.

      And if I start discussing a “logarithmic scale”, eyes will glaze over …

      So my writing is a balancing act. I want to put in enough information and links so that people who want to dig deeper about some part of the story can do so, but not so much information that people turn away.

      Next, you say:

      The real part that defies me is similar to many studies. The study doesn’t seem to have any data about laboratory testing to determine ranges of pH and their affect on the crabs. It would seem data from a carefully “controlled” group of laboratory tested subjects at various pH’s would provide a standard to judge ocean caught subjects against. As it is, they are attempting to collect info on two variables at the same time.

      Mmm … it sounds like a good idea, but there are lots of issues with this suggestion.

      I call these kinds of studies “aquarium studies”, and they all suffer from a common flaw— aquarium ≠ ocean.

      Doesn’t mean that they are useless, but in the real ocean there are lots of variations in the whole carbonate chemistry universe—argonite saturation state, pH, salinity, total alkalinity, temperature, dissolved inorganic carbonate, phosphate concentration … are we seeing a problem yet? … Revelle buffer factor ( dln(pCO2)/dln[DIC] ), pressure, silicate concentration, total boron, pCO2, chemical buffer factor ( dpH/d[DIC] ), ammonia concentration, the list goes on and on.

      Then there are the pressure-related buffering systems of variations in the carbonate compensation depth and the aragonite compensation depth, not to mention the lysocline … these occur at a pressure of around 5,500 psi (380 bar). How are you going to model those?

      And that doesn’t include the effect of marine life itself. Coral reefs control the pH of the water flowing over them, and I find the following:

      Marine life is already able to buffer drops in pH, finds new research in Scientific Reports. “Our research shows that marine life plays a substantial role in controlling the level of acidity, or pH, along the coast just by breathing or photosynthesizing,” said Nyssa Silbiger, an assistant professor in the Department of Biology at California State University, Northridge and lead author on the new study. “Marine plants and algae increase pH in the seawater right next to them, making it more basic, while animals make it more acidic.” “This is an exciting result because it shows that marine life not only respond to changes in pH, but that they actually play a major part in controlling it,” Silbiger said.

      Underlying article is Biophysical feedbacks mediate carbonate chemistry in coastal ecosystems across spatiotemporal gradients

      So it’s far from a simple problem to do “laboratory testing” on the effects of changing oceanic carbonate chemistry.

      w.

      • Very glad to read this comment.
        I know I am not crazy, and this is my understanding as well.
        It is so complex in fact, that I am sure the only practical approach is to observe what is happening with the sea life.
        There are only a few things I am sure of, and among them is that there is a large degree of bias in how all such matters are written about and even studied among a large number of groups and individual scientists. In short they cannot be trusted, IMO, as a group.
        No one should be believed simply because they think something is true under any circumstances, but this is not any circumstance. So there is that.
        Another thing I am sure of is that besides for the level of CO2, nothing that is occurring is outside of the range of recent historical variations.
        Another is that the biosphere is built out of CO2.
        And another is that the idea that the preindustrial levels of temperature, CO2, or any other parameter were not some Goldilocks state of the environment and any changes will be bad.

      • “Marine plants and algae increase pH in the seawater right next to them, making it more basic, while animals make it more acidic.”

        WR: This one sentence shows that the stabilizing system already is incorporated in the life cycle in the oceans.

        This pH stabilizing process is of more importance than the dissolving at great depths (below the lysocline) which is a process that works on the geological time scales of tens and hundreds of thousands and millions and tenths of millions of years. Life creates its own pH and where pH is low Life finds its own solutions.

        The swan mussel shows that life can create chalk and protect the shells well enough to survive in real acidic circumstances. (see comment below, https://wattsupwiththat.com/2020/01/31/the-solution-to-dissolution/#comment-2907291)

      • Willis, Thanks for the reply. With all the variables you point out, it should be difficult to isolate the cause of change down to just one, CO2 caused pH changes.

    • You may be corrects, but I cannot find that definition of the word.
      Rather from the FreeDirectory:

      … to lower in character or quality. Debase implies reduction in quality or value: “debasing the moral currency” (George Eliot).

      • It’s a pun. “Base” means low in character or quality. It also means it has a pH higher than 7. If you lower the pH, you are making the solution less basic — de-basing it.

  10. Thanks Willis,
    Good stuff as usual, thanks for the enlightenment.
    About your comment :
    “..Care to take a guess at the pH of the 6% solution of sodium hypochlorite, which is what they used to dissolve the carapace epicuticle? ”
    I believe that’s the stuff my pool guy uses to discourage fish. I have however had an aligator move in once and a couple of ducks that drop in for an early morning dip quite regularly, so it can’t be that dangerous!
    Cheers
    Mike

  11. I might add here for general interest in your own innards that our body fluids are maintained slightly alkaline also — very near pH 7.4; with much deviation lower (acidosis due for example to excessive metabolic acid production or CO2 retention from respiratory insufficiency) or upward (alkalosis due for instance to gastric acid loss from vomiting, excessive antacid ingestion, or hyperventilated respiratory expulsion of CO2) initially defended against by the buffering capacity of resident bicarbonate, phosphate, and amino acid polymers in those solutions, and then ultimately readjusted back toward 7.4 by your kidneys retaining or expelling bicarbonate or other excesses via urinary excretion.

  12. Everyday, for the past decade, first thing in the morning, I drink the juice of one lemon in a large glass of distilled water.

    Am I drinking acid? Yeah, sort of, but not really, because it’s not that simple. As conflicted as it might sound, after lemon juice enters the human body, it has an alkalizing effect. I’ve known this for lots of years.

    Things are seldom as straightforward as some would like to have us believe.

    Informative article.

    Off to make a glass of “acidade” now.

  13. Willis – I’m an engineer not a chemist but this is my musing on the subject…or am I out of my depth here ?

    The sea is effectively “buffered” by countless Quadrillions of tonnes of Calcium (Ca), Calcium Oxide (CaO) & Calcium Carbonate sediment (CaCO3 = limestone or the dead exo-skeletons of molluscs, coral, plankton etc.) the sea is actually slightly alkaline – it would require thousands of times man’s output (of various acid generating pollutants such as SO2) to neutralize this and push the seas towards “acidification”.
    Man’s pollution of the oceans is a very real threat but acidification by CO2 is simply a bogeyman, a distraction from real and pressing issues.
    Claiming that CO2 is the biggest threat to our Oceans when it is in fact either the weakest threat and possibly a great benefit – is distracting much needed funding and attention from very real and pressing issues – in this respect the AGW phantasm is very damaging indeed.

    The average pH of the sea is 8.2 (varies by +0.3 to -0.5 pH units naturally) – please note this is Alkaline it has to fall below 7.2 to be “Acid” so the term acidification is deliberately misleading – the sea can certainly become less alkaline but there is simply not enough Carbon around to turn the sea acidic.
    Alarmists like to say things like “We are turning our seas to acid” – which is pure alarmist “sound bite science” calculated to frighten the scientifically ignorant.
    The alkalinity of the sea certainly varies with CO2 concentration but CO2 concentration varies with temperature of the sea – Henry’s Law (and virtually nothing else).

    https://wattsupwiththat.com/2015/01/02/a-neutral-view-of-oceanic-ph/

    Just to further emphasise the highly buffered nature of the sea, man places millions of tonnes of Sulphur Dioxide SO2 into the atmosphere where it combines with water H2O to produce Sulphuric Acid (Battery Acid) H2SO4 or “acid rain” – and we continue to do so.

    SO2 pollution production peaked at about 55MT in 1978 and is now down to about 30MT and falling as nations wisely keep on reducing this pollutant (that’s why “green” diesel is advertised as being low Sulphur 50ppm, 20ppm or 2ppm – the refineries have to extract it and coal fired power stations have to use scrubbers to remove it etc. etc.).
    My point is that Sulphuric acid is billions of times more potent than weak carbonic acid and it all ultimately falls into or drains into the sea.

    (pH is a measure of positive Hydrogen ions and is actually not a good indicator of the overall “strength” of an acid or alkali – “strength” is generally considered via its Ka rating (dissociation constant).
    Ka equivalent rating: Sulphuric Acid H2SO4 is 1.0 x 10^3 which is 2.27 Billion times stronger than Carbonic Acid CO32- is 4.4 x 10^-7 (which is quite pleasant to drink – soda water – common to all fizzy drinks – is as “bad” as it gets).
    So H2SO4 acid rain represents a threat 2.2 billion times worse than man’s CO2 production and the seas soak it up without so much as a blip in its pH.

    https://en.wikipedia.org/wiki/Acid_dissociation_constant

    (Consider Nitric acid { HNO3 } produced by lightning strikes, ±5-10 million tonnes PA which has a Ka equivalent rating of 2.4 x 10^1 which is equivalent to 11-22 billion tonnes of CO2 or approximately 1-2 times man’s production of CO2 as far as ocean acidification is concerned.)

    Now I ask you how significant CO2 savings can possibly be when our average annual reduction in H2SO4 exceeds the effect of all the CO2 man has ever placed in the atmosphere (inasmuch as the effect it has on “ocean acidification”) since man discovered fire.

    The concept that the seas, which are buffered by Quintillions of Tonnes of Calcium / Calcium Carbonate / aragonite, could ever become acidic is so far fetched as to be considered scientifically delusional.

    • Thanks, Ken, all good stuff. One note of interest.

      Thirty million tons of SO2 added per year will all come back down, as you point out. However, this is about 0.06 grams per square metre of earth’s surface area per year …

      So I suspect it’s what I call a “difference that makes no difference”.

      Regards,

      w.

      • There is a difference as far as agriculture is concerned.
        Sulphur deposition from the atmosphere in the UK has declined since the late 1960s to the extent that farmers now have to use fertilisers with added sulphur to grow decent yields of crops.

    • Ken,
      I wanted to point out a few things.
      In your chat you said that carbonic acid is CO3 ^-2, which represent one carbon, three oxygens, doubly ionized so it has a minus 2 charge.
      This is incorrect.
      That ion is called carbonate.
      It is present in exceedingly low concentration in a solution of Co2 in water.
      Good thing.
      Carbonate is a very strong base.
      Recall that the conjugate base of a weak acid is a strong base.
      Carbonic acid is H2CO3.
      It’s conjugate base is bicarbonate, HCO3-.
      Only 1.7 of every 1000 molecules of CO2 is present as carbonic acid, which itself has a low dissociation constant…that is why it is called a weak acid, only a part of it dissociates into ions. A small part.
      The equilibrium is as follows.
      H2O + CO2 ⇌ H2CO3 ⇌ H+ + HCO3
      The species above are, in order, water, carbon dioxide, hydrogen ion, and bicarbonate.
      This is what exists in sparkling water.
      Only a tiny amount of the bicarbonate is further dissociated into carbonate (it is an even weaker acid that carbonic acid) and another hydrogen ion…which exists as hydronium and not a free proton, so there is barely any carbonate ion in any common solution of CO2 and water, such as the ocean or rain or soda pop.
      Good thing, getting back to the conjugate base thing…a solution with only carbonate and water would dissolve your mouth, since carbonate is the conjugate base of a weak acid, it is a strong base. About like lye, sodium hydroxide. The carbonate would pull protons off water and make a caustic solution.
      We called it carbonated water, but that is only a figure of speech, an idiom.
      The amount of carbonate in a CO2 solution is negligible.
      The Ka you listed is for the first dissociation of carbonic acid to bicarbonate and hydrogen ion.
      It is the Ka for H2CO3.

      Next discussion:

      Chemists discussing the pH of various solutions typically do not use the term “alkaline” to refer to a solution with a pH above 7.0 (7.2 is not the dividing line, as you imply…7.0 is).
      Instead, they use the word “basic”.
      It is not entirely and necessarily incorrect to use the word “alkaline” as you do, but it can cause confusion.
      Above 7, basic.
      Below 7, acidic.
      At exactly 7.0, neutral (although some sources list neutral as a range close to 7.0 on either side…since being logarithmic such small variations from 7 are in many circumstances inconsequential.

      The pH scale originates from the fact that plain water, H2O, has a dissociation constant: At any moment in time, some of the molecules are not floating around as H²O but as H+ (which do not exist as free protons but as hydronium ions H3O+) and OH- ions.
      The dissociation constant is 10 to the minus fourteenth power, 10^-14.
      And since pH is equal to minus the log of the hydrogen ion concentration, which is exactly half 10^-14, or 10^-7 (still in plain deionized water), the pH of pure deionized water is 7.

      The reaction, which is an equilibrium reaction, is thus:
      H2O + H2O ⇌ H3O+ + OH

      Knowing these few details helps one get a clear idea in ones head about what exactly is being discussed when talking about pH.
      As someone above has pointed out, alkalinity means something distinct in certain situations (such as the common lingo used regarding swimming pool chemistry and such) , which is why it is better to speak of basic solutions, rather than alkaline ones, if one simply wants to refer to solutions in a given pH range.
      Also, if you look it up, you will find sections in every chemistry text called acid-base chemistry, for the very reason I am describing.
      Not a criticism, just a clarification.
      Since the subject is using clear and precise language as used by actual practicing scientists, being concise is best.

      Also worth mentioning that when CO2 is dissolved in water, the vast majority of it does not exist as carbonic acid or any of it dissociation products, but as a dissolved gas.
      This relationship between dissolved gas and carbonic acid is described by the hydration equilibrium constant, K sub H (I used to have the codes for all the important sub and super scripts, but lost them when I reset my computer last week…doh!), which in plain water is 1.7 x 10^-3, and in sea water is even lower at 1.2 x 10^-3.
      So only about 1 or 2 molecules in every thousand are actually in the form of carbonic acid, which then dissociates into the various ions it is in equilibrium with.

      • I see tha when I wrote this:
        ” The equilibrium is as follows.
        H2O + CO2 H2CO3 H+ + HCO3-”

        WordPress did not print the sets of arrows which make it clear what is going on with that equilibrium reaction.
        But for some reason it did here:
        “H2O + H2O ⇌ H3O+ + OH−”

        Although in both of them it made the plus and minus superscripts into regular plusses and minuses, which makes it confusing as well.
        Not sure why.
        I’ll see if I can figure it out and post them so they are more clear, and maybe Willis will once again be kind enough to correct the originals in the post.
        In the first one there should be two sets of equilibrium arrows, like this:
        H2O + CO2 ⇌ H2CO3 ⇌ H + HCO3-

        Gotta reload all those symbol unicodes…it is much more clear when the proper symbols are used…plus superscripts for ions w/ single positive charge meaning one electron has been removed, -2 as a superscript for double minus charge indicating two extra electrons are available for covalent bonding, etc, numeral subscripts to indicate the number of atoms of something in a molecule, etc.
        And equilibrium arrows, ⇌, to indicate that a reaction is reversible and will respond according to Le Chatelier’s Principle when conditions are changed, e.g. if some acid is added to the solution, or more CO2 becomes dissolved into the water, etc.

        • Thanks for that – like I say I’m an engineer not a chemist – but I’m at least not completely off my trolley.

      • The Ka Ken listed for carbonic acid is, as I noted, the correct Ka for the first dissociation into bicarbonate and hydronium, but this point needs clarification.
        I thought I would also point out what order of magnitude the various species that CO2 is in equilibrium with exist in .
        4.47 x 10^-7 is the apparent dissociation constant.
        That Ka is must be understood to include the total amount of CO2 present, and so it takes into account the hydration equilibrium constant of 1.7 x 10^-3.
        The first Ka of just carbonic acid, not including the free CO2 gas which is the bulk of the CO2 present, is ~ 2.5 x 10^-4

        And then there is the second dissociation constant, which describes the relationship between bicarbonate and it’s equilibrium with carbonate and hydronium, and it is a far smaller number than even the apparent Ka.
        It is equal to 4.69 x 10^-11
        This is a tiny number, and is relative to the amount of bicarbonate, which is a tiny number compared to the amount of carbonic acid formed, which is very small compared to the amount of CO2 present in the water.
        The n one must consider what happens in actual solutions when other things are present that change the pH.
        Where CO2 and it various reaction products with water are the only things present, the solution is acidic and CO2 is the dominant species, as noted.
        But the situation changes entirely when the pH is being affected by other substances present, and especially when the pH is not acidic due to these other substances. Everything changes, from the Ka values to which species is dominant and how much of each is present.

        At the pH present in the oceans, bicarbonate is dominant, and at higher still pH, carbonate is.
        There is a graph which shows how they all vary at differing pH levels.
        It has to be kept in mind that a lot of other stuff is also in the ocean, and species are being added and removed by numerous processes, the various species are also in equilibriums with other things present as well, and the temperature is changing which changes the Ka values, and how much CO2 can be dissolved into the water (which is still another equilibrium not mentioned yet).
        So this plot is not what happens in the ocean, per se, but is only generally true for various pH levels.

        Here is a link to a discussion in Wikipedia on the subject.
        Be cautioned that it is, you know, Wikipedia, and this is a controversial subject having to do with climate alarmism:
        https://en.wikipedia.org/wiki/Bjerrum_plot

      • Also worth mentioning that when CO2 is dissolved in water, the vast majority of it does not exist as carbonic acid or any of it dissociation products, but as a dissolved gas.

        This is true for pure water but not seawater, in seawater bicarbonate is the dominant species.
        When pCO2 in the air is increased the concentration of CO2 in the water increases (Henry’s law) and the equilibria shift leading to an increase in H+ ions (decreasing pH). In chemistry increasing the H+ ion concentration is termed ‘acidification’, only if it carried out in aqueous solutions to balance OH- and H+ is it termed ‘neutralization’. The correct terminology is acid/base, alkalinity is something different, Total Alkalinity (TA) in seawater is the balance between H+ and other important ions:
        AT = [HCO3−] + 2[CO32−] + [B(OH)4−]+ [OH−]+ 2[PO43−]+ [HPO42−] + [SiO(OH)3−] − [H+]− [HSO4−]

    • I would note that sulfate (at ~0.3 mass%) is the third most abundant ionic species in sea water behind Na+ and Cl-.

  14. Willis and others
    Some points to be made: A reason that the Monterey Bay Aquarium monitors its water intake is that in the past they lost a lot of their fish stock when they brought in water with low oxygen and low pH. Water upwells from the very deep Monterey Canyon and the pH can change dramatically within a matter of minutes. Yet, life has existed along the coast since well before the prolific use of fossil fuels by Man. The upwelling water is ‘fossil’ water that is hundreds of years old, and reflects both past atmospheric CO2 levels in high latitudes, and the abundance of oceanic life, which when it dies, releases CO2 generated by decomposition, into the cold, high-pressure (deep) water. The decomposition also reduces the oxygen concentration. The coastal environment is challenging for life, but a balance has been struck between the fluctuating pH and the abundance of nutrients supplied by the upwelling water. These disingenuous claims about the hardships of larvae imply that humans are responsible. Instead, it is an example of life pushing the boundaries of where it can survive, with costs and benefits swinging back and forth. Even if the small, slow changes in the surface pH of the open ocean were a serious concern, we aren’t sure it is valid because the historical data have been ignored and a model substituted to calculate what the past average pH presumably was. [That has been documented here on WIWT.] However, that claimed small, long-term pH change is dwarfed by diurnal, seasonal, and weather induced pH changes in coastal upwelling environments!

    • Thanks, Clyde, all true. I fished commercially in Monterey Bay for five years. The Monterey Canyon has a huge influence on the area. Here’s why:

      This shows Monterey Bay. Santa Cruz is at the top of the bay. Moss Landing is at the tip of the submarine Monterey Canyon. Monterey and the Aquarium are at the bottom of the bay. And as you point out, the Monterey Canyon funnels upwelling water into the whole area.

      w.

  15. Every alarmist climate change claim is now steeped in pseudoscience or outright fraud (lies). I’m not talking about climate change itself, the slow temperature response of the atmosphere-ocean system to a minor LWIR forcing increase. I’m talking of the alarmist narrative the Socialist Left has now adopted because their attempts to remain grounded in science and observation were for decades going nowhere in terms of public awareness or concern. So in the past 5 years, they’ve turned-on the spigot of alarmism as they see their Globalist-socialism scam about to unravel as the 35-40 year warming phase that began circa 1980 is coming to a close. Everything climate change now has to have a pseudoscience alarmist claim, whether’s slow steady SLR, or Arctic warming, or some tropical storm somewhere. And with Springtime in the US now approaching, so too is tornado season. With this being an election year of pivot importance to the climate scammers, you can bet every tornado outbreak in the next 5 months will be blamed on climate change.

    Either it’s a cherrypicked start date to make some alarmist claim, or some other outright lie is claimed like Willis exposes here on the Guardian’s absurd fraudulent claims on OA.

    What the Guardian is doing of course with all their alarmist claims is continually repeating the lie (mythical OA dissolving crab shells in this case) to achieve a propaganda effect on people who should know better. Then over time the insidious effect of continual bombardment with the lie, they actually starting to believe the lie and then to pass them along as well. The lie becomes indistinguishable in the public consciousness from truth or scientific facts. They even enlist movie stars, folks who typically have less education than Greta Thunberg, to parrot the claims in exchange for some virtue points in the pop culture, The movie star is being environmentally aware or “woke” and it gets them lots of “likes” on social media for example. Their publicists and agents are then happy too.

    All of this is very similar to what we know how dietary science claims are passed around, gain some credibility from a TV-Hollywood celebrity pushing its value. The diet becomes a new fad for a while until problems start to arise, or some new fad comes along. Practically every dietary fad, if not all of them, are laden with pseudoscience and junk claims.

    All of this is climate scam is now being pushed by big money from the GreenSlime “behind the curtain.” If you don’t think so, then simply look at a Billionaire like Michael Bloomberg. He has spent $100 Million of his own money on advertising in just the last 2 months for his run at the Democratic Party’s nomination and to bash Trump.

    If Mike Bloomberg has this kind of money ($200 million spent in just 2 months) to spend on his own advertising campaign, so too do other billionaires like Steyer, Soros, and a host of other Giga-rich Elites pushing the climate scam have what to you and me is are vast fortunes to spend on pushing climate propaganda like the OA scam from the Guardian. Somewhere along that path, the Guardian’s owners and editors are getting bought by the GreenSlime. And like the LA Times case, it’s owned outright by a GreenSlime billionaire who has a deep investment in the battery market.
    As for the Democrats, the Leftist academics, and the other media outlets they are lining up at the billionaires’ teats for their share of the GreenSlime milk. The victims of course are all of us, the middle class, who they hope to fleece with ever higher electricity bills and unaffordable fuels for our vehicles, and us push into serfdom. The are costs that the elitist class can easily afford, but they put you and me into poverty and rips away our affluence to afford vacation, nice cars, and a secure retirement. We are, after all, the “deplorables” in their estimation.

  16. It’s ironic that the source of earths acid rain is hydrogen sulfide emitted by the ocean (plankton). Without this constant condensation nuclei, clouds and rainfall would be unlikely without other factors like dust/volcanoes.
    The acid rain dissolves minerals on the surface, made more accessible by UV sunlight decomposing minerals, and feeds root systems of plants. A natural fertilizer. The pH is neutralized quickly with the exception of violent thunderstorms which vigorous lightning fixates the oxygen/nitrogen in the atmosphere creating new compounds in large enough amounts to be blamed on runoff from farms. Nitric acid will flow into rivers creating an algae bloom called a “dead zone” which is actually an “alive zone” that will clog the gills of large schools of fish who feed off the plankton. (water not deprived of oxygen)
    Indeed, the entire ocean bio system benefits from the so-called dead zone as micro nutrients feeds the entire biosphere from the top of the food chain to the bottom. Benefits of acid rain fall.

    I once put some seashells in some carbonic acid (club soda) in a pressure container to dissolve the shells, it didn’t work. Apparently carbon does not dissolve carbon?
    I remember in a science class the question was asked what it would take to raise the pH in the ocean to a neutral seven. After calculating all known sources of hydrocarbons on earth, there wasn’t enough carbon on the entire planet, when mixed with the volume of water in the ocean, to bring it to an acid state.
    The only possible theory how this could be accomplished is to first, eliminate all life on the planet.
    Then lightning will do the rest as it converts the nitrogen in the air to nitric acid to fill the oceans after a few million years.

    By the way, hydrogen sulfide, which is natural, is a kissing cousin to sulfur dioxide, which used to be in regular gasoline before it was outlawed in favor of unleaded to prevent photochemical smog in LA. and the rest of the nation.
    The fuel undergoes purification, boiling away the hydrocarbons leaving Sulphur and other contaminants behind. I asked refinery workers what do they do with the leftover Sulfur sludge? He pointed up. They used to put it in red fuel for off-road use only, and road tar, but most of it goes into the wing fuel tanks of jets because sulfur is a combustible fuel, an octane booster, increasing thrust. The pollution is spread over such a wide area, the EPA parts per million doesn’t apply at the altitude and speed that jets deposit in the atmosphere. ( they can’t put it back in the ground, no other practical solution, other than burning, is available)
    The sulfur will attract water vapor from the humidity in the upper atmosphere forming clouds. This is why the contrails quickly disappear when they pass through an area of low humidity, while getting thicker near cloud formations. Chem trails.
    Other chemicals are added to the fuel for the purpose of disposal. Not in such large amounts to put the safety of the plane at risk. The composition of the chemicals in fuels for the center tank, which is used for lift off, is regulated country by country. The information is available on the Boeing website.

    • Got a problem with the implication that exhaust products from jet fuel cause the contrails in the sky. I have been amused to see them from gliders — no fuel of any kind involved.

      The contrail is ice particles precipitated by the turbulence of the wind-tip vortices; how long it sticks around before being sublimated depends mostly on the “lapse rate”, so glider pilots like to get up there for good lift on the days when they see contrails persist.

    • “The composition of the chemicals in fuels for the center tank, which is used for lift off, is regulated country by country.”
      Nonsense, there is no differentiation in fuel between tanks in an aircraft.

      • I found too much nonsense in that post by max to bother with at this hour.
        Leaded gas contained lead…usually something like tetraethyl lead.
        That whole post was verging on being a veritable Gish Gallop of misinformation and flat-out wrongnesses.
        There are all sorts of things that act as condensation nuclei, and one of the more common ones is salt…from the oceans. Tiny salt crystals. Or dust from deserts, any sort of dirt or clay that becomes airborne, microorganisms of various sorts and sources. There is no shortage. Every droplet in every cloud is thought to require one. That is a lot of droplets. But hydrogen sulfide is a gas, just molecules. Condensation nuclei are bits of solid stuff on the order of a tenth of micrometer or more in diameter.
        And hydrogen sulfide mainly comes from decomposition under anoxic conditions…like the muck at the bottoms of lakes and such. It is what gives rotten eggs their smell. The stuff some people have said that plankton sometimes release is dimethyl sulfide. This idea is tied up with James Lovelock’s CLAW hypothesis.
        The amounts of condensation nucleii is typically measured on the hundreds to thousands per cubic centimeter.
        Rain is acidic due to any number of gasses in the air, such as CO2, or SO2, or NO, or NO2.
        But mostly it is CO2, which although a small amount of air is far more than any of those others, and it is everywhere, all the time, for all practical purposes.

        The rest is a similar conglomeration of semi-facts and outright bullshit. Ocean eutrophication is very real, and when water is depleted of oxygen, fish die. It starts out as an algae bloom, but as they decompose they use up all the available oxygen in the water column.

        High sulfur stuff called bunker oil was until recently used in ships, but it is now illegal by international law, unless they extended the deadline. Whether some people cheat, who knows.
        Sulfur is not a significant source of energy in hydrocarbon fuels.

        Contrails form from the exhaust from planes, since burning any hydrocarbon produces water vapor. If the humidity is high enough, the extra water vapor will condense as it cools and persist for some period of time. The pressure wave that travels along with planes can also cause brief condensation in very humid conditions, and may enhance the formation of contrails.
        There aint no chemtrails…it is condensation.
        Life must be simple but sometimes scary for the misinformed.

  17. The other part of acid-base chemistry going on here in seawater is buffering capacity. Pure water without any buffering agent like bicarbonate, is easily pushed to wild pH swings with even small additions of a base or acid. This is simple Chemistry 101 Lab stuff that so many people never took in high school or college, or if they did they forgot it.

    Around all the oceans on the continental shelves many places a have deposits of chalk and limestone, which is almost entirely calcium carbonate. And calcium carbonate is basic. And then their is the deep spreading rift zones in the oceans, which are layers of basalt. Ever wondered how that name arose? Basalt is mostly olivine and pyroxene, which are alkali in character, hence the name “basic salt” reduced to basalt.

    The oceans will never become acidic except in very small localized areas where possibly sulfur introduction from volcanic vents is overcoming the very high alkali buffering of the oceans and their basins.

      • I was wondering about that too.
        I took a lot of geology classes, and never once heard anyone mention that.
        In fact, I have read stuff about geology almost obsessively my whole life.
        It is the real world, not some made up crap, youknowwhatImean man?

    • ” Basalt is mostly olivine and pyroxene”

      Basalt is predominantly plagioclase feldspar with subordinate pyroxene and iron oxide (or iron/titaium oxide). Olivine may or may not be present as may numerous minor minerals.

      The origins of the word “basalt” has been traced back to the Egyptians. It has nothing to do with “basic salt”. The use of the word “basic” by petrologists has nothing to do with the pH.

  18. Rain has a PH of about 5.6 while pure distilled water is neutral at 7.0. So rain water is actually acidic, if using the terminology correctly.

    I have often wondered if cooler rainwater in the tropics in shallow waters growing coral isn’t more affected by the lowering of the shallow ocean water PH from heavy rain, which in general the global ocean is averaging 8.1 but as mentioned in the article it can be all over the map at different depths and locations.

    Wouldn’t it be ironic if we discover that some of the coral bleaching events are caused by a lot of rain in a specific area that has been subjected to bleaching setbacks, perhaps maybe as well when the Nino/Nina oscillations are changing sea levels locally over a period of a few years during heavy rain events. A foot of heavy cool rain with a Ph of 5.6 in relatively shallow water will make a short term difference to local ocean Ph over a short period of time, perhaps long enough to affect coral health. There is probably more than 1 reason for coral set backs than just trying to blame everything on our small beneficial increase of fossil CO2.

    • Rainwater is slightly acidic because it is pure deionized water with some gasses dissolved in it, some of which form acids when in solution.
      Once it hits the ocean, it comes into contact with a hugely larger volume of buffered solution.
      And since what causes most of the acidicty in rainwater in unpolluted air is CO2, it is exactly the same as the subject at hand…small changes in the concentration of CO2 has a de minimis effect on ocean pH.
      Rivers discharge the rainfall from entire geographic regions into a single spot of the ocean.
      The effect is local, as the dilution factor is enormous within a few mile to tens of miles of the mouth of the river.

      Of course everything hasthe possibility of having an effect on corals…the pH of the ocean, rivers, temperature, salinity levels (which often correlate with the concentration of other dissolved substances besides salt), and pollutants such as excess nutrient runoff and even such things as sunscreen from people swimming in the ocean after slathering themselves with that crap.
      And as you mention, water level.
      The thing not mentioned by alarmists when they are in their coral bleaching panic mode, is that coral bleaching is a normal and ever-present phenomenon with corals.
      They do it whenever the corals are stressed beyond certain limits, and the algae symbiont living with the polyps is expelled. It is a protective mechanism for the coral.
      It is estimated that 10% of all coral on Earth have always bleached every year.
      Typically, the coral reacquires a strain of algae that is better suited to the conditions which are present, and everything is fine.
      Bleached coral are not dead…although they can and sometimes do die.
      However, corals also reproduce in vast profusion, and in such numbers they can be seen from space.
      Also, they do so in a coordinated fashion, and in so doing give rise to incredible genetic diversity between interrelated species of algae, which is one of the reasons that even dead corals are commonly recolonized with new polyps and are, once again, fine.
      The people who have taken it upon themselves to be the panic mongers for the human race almost never have significant knowledge of the very well understood life cycle and ecology of corals and coral reefs, and how the Cnidarian class called Anthozoa make reefs consisting of a multitude of tiny individual polyps, which themselves live in a state of symbiosis with little single celled algae called dinoflagellates, specifically a diverse genus called Symbiodinium.
      These algae exist in huge profusion and genetic diversity themselves in the ocean, and when ingested by the polyps, they take up residence in the cells of the host, and provide the products of their photosynthesis to the polyp and in turn are supplied with the nutrients they need to live.
      More commonly called zooxanthellae, the algae are adapted to specific environmental conditions, and when the conditions change, the zooxanthellae can become a burden for the polyps, taking more than they give back. The polyps then expel them as a survival mechanism.
      Since the zooxanthellae are dinoflagellates, there are always some just swimming around in the water, and the ones best adapted to specific conditions will be most prevalent and numerous, so that as the polyps feed by filtering passing water, they ingest new zooxanthellae which will be retained if they are suitable to the polyp. During the period when there are no symbiodinia present in the cells of the polyps, the corals look pale but are not dead…they are called “bleached”, but not because of any actual damage, just lack of color. The polyps do not need to be colonized to live, but without them they are not very vigorous and usually eventually die. More commonly before they die they acquire new symbionts.
      It is amazing to find out how little some people know about this stuff, and I mean even the people who are the supposed experts on the subject.
      They act as if a bleached reef is dead, and dead forever.
      In fact there is a wealth of literature going back to as long as people have been studying the oceans on corals being damaged, bleached, whatever, and then rapidly recovering, spreading out, colonizing new areas, etc.
      One of the most amazing spectacles in nature is when corals spawn. They do so at the same time on the same night or nights, even among different species, typically on a New Moon, often in Spring.
      Within minutes, crystal clear water can become opaque with a combination of eggs and sperm, across hundreds of miles.

      There are some great TV shows on film showing it, and many on you tube.
      Here is one:
      https://youtu.be/eO_2JJynlOA

      Glad no one told the people who made this film that the GBR was dead…they might have stayed home and missed the show. Note how even the people who made this show do not know much about the biology of coral, mistakenly stating that corals are bleached due to lack of nutrients.
      It would be a much more interesting show if they described and filmed the whole story.

      On my Twitter page I have amassed a collection of news articles describing how various reefs have recovered after being bleached. In nearly every one of them, astonishment was expressed that recovery was possible, as one can find just as many if not more stories about how when they were damaged…from hurricanes, tsunamis, you name it…they were assumed to be, and declared, dead.
      Life is resilient, and creatures which have survived for hundreds of millions of years have lived through worse than a few tenths of a degree of warming.
      In fact…the corals of the GBR are the same ones found in far warmer waters in places hundreds of miles closer to the equator!
      You would think that would be a clue.

      • Golly, another typo…I am blaming auto correct this time…no way I typed infect instead of ingest.
        This:
        “These algae exist in huge profusion and genetic diversity themselves in the ocean, and when infested by the polyps…”

        Should be:
        “These algae exist in huge profusion and genetic diversity themselves in the ocean, and when ingested by the polyps…”

        • Fixed, but you have a typo in your typo. You didn’t type “infect” as you claimed, so it took a minute to find it.

          w.

          • Thank you Willis.
            That made me laugh.
            See, I got in the habit of making a typo when I point out that someone else has made a typo, just to let everyone know I was not being pedantic.
            Just that I was, you know, a really bad but aspiring comedian.
            But that time it was unintentional.
            I guess I should be glad it was not something with obvious Freudian implications.

  19. Hi Willis,
    interesting reading as always. One thing I discovered while maintaining my salt water fish tank, is that the pH of the tank water would vary between night and day without me doing anything to the water/tank. (Note: I no longer have the tank or I would take some readings to get actual pH readings.) I wonder how much the day to night swing in pH is with the ocean? I know the ocean has more factors in play than the nearly closed system of my fish tank did but think the swing between day and night would be at the very least noticeable.

    Cheers!

    Joe

  20. One other interesting point learned many years ago is the the pH scale is logarithmic, not linear, and shows the exponent (sign inverted) of the concentration of hydrogen ions in the solution. (I took chemistry to degree level). Neutral solutions have a concentration of hydrogen ions as 10^-7, lemon juice (per Willis’ graphic above) has a concentration of 10^-2: a 100,000 fold difference, not a five fold difference. Similarly, the difference between pH8 and pH7 is a ten fold change of the concentration of hydrogen ions.

    The ocean is also naturally buffered, meaning that there are chemicals in there that slow down changes in pH from adding other sources with high or low pH (i.e. alkalis or acids). CO2 in solution makes carbonic acid, an extremely weak acid, so it isn’t going to make a great difference with small changes in concentration.

    • In the ocean, only 1.3 molecules of CO2 which are dissolved in the water are in the form of carbonic acid and it dissociation products.
      The other 998.7 molecules out of that thousand are simply CO2 as a gas floating in the water.

  21. Not enough data for the Pacific Willis? Here’s a start. The Ph of the ocean inside the Great Barrier Reef near Cairns ,reads above 9 and hasn’t moved in the last 10 years.

  22. The dishonesty of reporting about the so-called acidifying of the oceans as part of the climate hysteria has constantly annoyed me.
    In agriculture, soils are classified strictly according to their pH levels and identified in accordance with that. When steps are taken to change the pH levels it is described as raising or lowering the pH levels or as reducing the acidity or the alkalinity of the soil in accordance with the desired outcome.
    All I can put the difference in approach down to is that with the soil, the information is being provided to those who work with the soil and have a practical understanding of it, whereas the information about the oceans is structured to appeal to the climate alarmists who on the whole have little or zero understanding of the subject and only respond blindly to whatever climate propaganda is prepared for their consumption.

  23. That was something that annoyed me when we visited the Baltimore aquarium some years ago. There was some young woman droning on about ocean acidification and my wife asked, “The ocean is getting acidic?” I said no, it’s getting less basic, maybe. I said there’s no way for it to become acidic unless runoff from ALL the continents somehow stopped all at once, and even then I wasn’t too sure.

    These people who spout this nonsense aren’t scientific at all. It’s really annoying.

  24. Thanks Willis for another great science class. A slight, possible Neutralization versus a scary, false Acidification was a great ah-ha moment for me. Thanks for the lesson on ocean pH.

    • And thanks to you, Drew. Inter alia, it’s comments like yours that encourage me to keep writing up my research.

      w.

  25. All of this hype is rather silly since we know that during the past, the planet was some 10, and perhaps at times, as much as 17 degC warmer than today, and at times had CO2 levels exceeding 7,000 ppm and ife on this planet, and in the oceans thrived. Indeed, the great explosi0n of life was during the Cambrian period when CO2 was circa 7,000ppm.

    During the Devonian period, CO2 was around 4,500 ppm and the oceans were around 30 degC. This era (some 420 to 350 million years ago) wqas known as the age of the fish. The oceans teamed with life and the largest fish ever to swim the oceans swam during this era.

    Further, ammonoids swam the oceans when CO2 levels were high, and they were rather big. See for example:
    https://ferrebeekeeper.files.wordpress.com/2012/03/104392973_da224cfc4a_o.jpg

    Given that CO2 was some 10 times that seen of today, and there was no adverse impact causing ocean acidification, we know that modest levels of CO2, even if they were to double to say 800ppm will cause no significant adverse impact.

  26. I love pickled onions. Anybody ever tried onions in a solution of Sodium Carbonate, or even just bicarb?

  27. Calling a lowering of alkalinity to be an increase in acidity is like referring to someone who is paying off a large debt “richer” after each monthly payment. They are not “richer” as they still have put away no money (wealth). They are slightly less in debt – that is all.

    Scare tactics are NEVER acceptable in hiding a truth.

    Climate “Science” (i.e. pseudo-science) is built upon a foundation of scare tactics. They violate every ethical boundary in science – tamper with data, hide data, hide process and procedure, exaggerate, and yes, make stuff up.

    It is one thing to believe in a hypothesis and be found wrong, and an entirely another to lie about the results in fear of being found wrong. These people are no longer scientists – they have become politicians.

    • Make stuff up is exactly correct.
      The term “ocean acidification was invented, made up from whole clothe, specifically as an alarmist tactic.
      Ever since it was, it is amazing how many people have glommed on to the hoax and come around insisting, INSISTING, that it is a correct usage of the word “acidification”.
      There are zero dictionaries in the world that define the word as meaning a lowering of pH.
      Because it never meant that.
      Dave Middleton explains ( I think it was Dave) the whole sordid story in several articles right here.
      Lemme grab one.

      Here we go, took me all of 26 seconds.
      There are others, but here is a small snippet quoted from the article and a link:

      “The phrase “ocean acidification” was literally invented out of thin air in 2003 by Ken Caldiera to enable liberal arts majors to sound sciencey when scaring the bejesus out of the scientifically illiterate masses. The geochemical process has been well-understood for about 100 years… But didn’t get a crisis-monger nickname until 2003.”

      https://wattsupwiththat.com/2019/07/25/the-total-myth-of-ocean-acidification-science-edition/

  28. The Guardian….

    – there are a few exceptions to the overwhelmingly dismal level of technical understanding of folk who write for them – I reckon though, that whoever dreamed up the Di-Hydrogen Monoxide prank scare was familiar with a lot of GMG output …

    Braying donkeys are in comparison positively cerebral.

    Here in the UK we also have the treasured BBC as the other cheek of the lefty alarmist ass – I expect some salaried producer / presenter combo/team has already reheated this bit of “OA” for inclusion in daytime TV, local programs, soaps, kids TV , Dr. Who and sports commentary.

  29. Propagada-ish papers like this one appear to get published easily.

    Science funding channels are administered by entrenched socialists within bureaucracies (bureaucrats are 95+% Socialist…the remaining 4-5% are Communists). Only Activist groups get funding and all that’s left after 30 years of that are Activist Scientists.

    This is where massive defunding and restructuring has to occur during Trump’s 2nd and 3rd presidential terms.

  30. Good post, WE. There has been borderline to actual scientific misconduct about ‘ocean acidification’ for many years, this paper being just another example. I explained the underlying seawater pH science (even used your Exkman transport diagram to explain Pacific coast upwelling) then documented two clear examples of scientific misconduct (Milne Bay corals in PNG and Netarts Bay oyster Hatchery in Oregon) in essay Shell Games in ebook Blowing Smoke. The oyster part was previously posted at Judiths under the same title.Cliff Mass picked it up and reblogged with his own take and followup research on the Seattle Times fake ’OA’ news on his U. W. weather blog.

    • Thanks, Rud, always good to hear from you. Someone upthread claimed that “acidification” was destroying oyster farms in the Pacific NW. I asked them for a cite … nothing to date.

      For those interested in Rud’s post on Judith Curry’s most excellent blog, it’s here.

      w.

      • WE, ty. You still have more ‘fire’ for this than I, after 11 years and at least parts of 3 ebooks. CtM, with whom I now have the privilege of lunching about monthly on our SF Atlantic beaches and InterCoastal, agrees.
        Highest regards to a long time climate science warrior.

        • Thanks, Rud. I’ve been beating this drum for almost two decades now, kinda getting used to the beat.

          Please pass on my best regards to CtM when you see him, he’s done an outstanding job with the blog. I hope to get down your way and see you guys at some point, don’t know when.

          Best to you and yours,

          w.

  31. Thanks Willis.
    I always enjoy your articles and learn things. I also enjoy the postscripts about your home conditions when you post an article here.

    We’re the same age, and my thought about this one is that in the years I have left in this life, I hope that I am never seated opposite a person at a dinner party who might want to pontificate about –
    Exoskeleton dissolution with mechanoreceptor damage in larval Dungeness crab related to severity of present-day ocean acidification vertical gradients

    • They never did mention in so many words that is, and certainly not upfront, that they were actually studying the mechanoreceptor of larval Dungeness crabs who had been severely injured by being soaked in a concentrated bleach solution until their outer cuticle dissolved clean off!
      Exactly how certain are they that concentrated bleach has no effect on them thar mechanoreceptors, I wonder?

  32. The level of acidity/alkalinity is expressed on the “pH” scale, where neutral is 7.0, alkaline is from 7 to 14, and acidic is from 0 to 7.

    There’s a difference between “alkalinity” and “alkaline”.
    “Akaline” is a pH above 7.
    Water with a pH below 7 can still have “alkalinity” that continues to resist a change to a lower or higher pH.
    Small point. The words are similar and related but don’t quite mean the same thing.

  33. I’ve just added a pinch of salt to my glass of CocaCola. I now have a savoury drink!

    Denier, unprecedented, emergency, extreme, doomsday….now acid(ificiation) goes into the “Dictionary for Warmists.”

    As an environmental scientist and geologist, I now sob daily for the increasing destruction of scientific principle – led by ignorant journalists who live by only one mantra these days “if it bleeds, it leads”. We live in an era of unprecedented knowledge and access to information – yet society in general has never been as dumb (in terms of the ability to think critically) as since before the Industrial Revolution.

  34. If you ‘believe’ in “ocean acidification” than you also must ‘believe’ that life in the oceans was impossible until Earth entered the ongoing Ice Age 3.5 million years ago. CO2 levels were just too high.

  35. The data from the “La Push” offshore buoy reminded me about a long blog post by Cliff Mass …

    Ocean Acidification and Northwest Shellfish: Did the Seattle Times Get the Story Right?

    “Other regional factors affecting ocean acidification in Washington include runoff of
    nutrients and organic carbon (such as plants and freshwater algae) from land, and local
    emissions of carbon dioxide, nitrogen oxides, and sulfur oxides, which are absorbed by
    seawater from the atmosphere. The relative importance of these local drivers varies by
    location. For example, acidification along the outer coast of Washington and Puget Sound
    is strongly influenced by coastal upwelling while acidification in shallow estuaries,
    including those in Puget Sound, may be particularly influenced by inflows of fresh water
    (which is naturally lower in pH than seawater) carrying nutrients and organic carbon
    from human and natural sources. The added organic carbon, as well as nutrients that
    stimulate excessive algal growth, can make seawater more acidic when algae and other
    organic matter decompose.”

    https://cliffmass.blogspot.com/2013/10/ocean-acidification-and-northwest.html

  36. To test if it is really becoming acidic, we should dunk authors’ heads in the ocean and ask “is it sour, is it sour?”

  37. I’m not good at chemistry, but from the first graph a correlation is obvious: apparently the alkalinity correlates with temperature — the deeper you go, the colder the water is, the lower the alkalinity is. The farther from equator you go, the colder the water is, the lower the alkalinity is. So, could it be that the alkalinity is a better measurement for the average temperature than using thermometers at too few points and trying to average their readings?

    • Interesting question, Luchezar. Actually, it’s much more complex than that. pH is a small part of the carbonate chemistry of the ocean. Here’s a glimpse of the various factors involved in pH.

      ALK — ALK, total alkalinity (mol/kg)
      Tinsi — In situ temperature in degrees Celsius
      Tlab — Measurement temperature in degrees Celsius
      Pinsi — In situ hydrostatic pressure in bar (surface = 0)
      S — Salinity
      Pt — value of the concentration of total phosphate in mol/kg
      Sit — the value of the total silicate in mol/kg
      k1k2 — “l” for using K1 and K2 from Lueker et al. (2000), “m06” from Millero et al.
      (2006), “m10” from Millero (2010), “w14” from Waters et al. (2014), and “r”
      from Roy et al. (1993). “x” is the default flag; the default value is then “l”,
      except if T is outside the range 2 to 35oC and/or S is outside the range 19 to 43.
      In these cases, the default value is “w14”.
      kf — “pf” for using Kf from Perez and Fraga (1987) and “dg” for using Kf from Dickson and Riley (1979 in Dickson and Goyet, 1994). “x” is the default flag; the
      default value is then “pf”, except if T is outside the range 9 to 33oC and/or S is
      outside the range 10 to 40. In these cases, the default is “dg”.
      ks “d” for using Ks from Dickon (1990), “k” for using Ks from Khoo et al. (1977),
      default is “d”

      I’m sure you can see the problems with using the pH to estimate the temperature.

      w.

  38. Think I have found the source of the problem:
    “This work was supported by the NOAA’s Ocean Acidification Program”.

    • Hilarious, thanks. The US Government scientists clearly know where the fame and the grants are located, and it’s not where good science resides.

      w.

  39. Great post Willis.

    The pH issue is a total cannard. The only thing that really matters is the aragonite saturation state. Adding CO2 lowers the saturation state, raising water temperature increases it. There’s no evidence at all that CO2 levels below 1,000 ppm pose any hazard to modern marine calcifiers… even above that, the hazard is speculative.

    • “The pH issue is a total canard. The only thing that really matters is the aragonite saturation state.”
      Exactly so. And so pH 7 is a canard too. The fact is that adding CO₂ shifts an acid-base equilibrium so that CO₃⁻⁻ is converted (molecule for CO₂ molecule) to HCO₃⁻. That reduces the aragonite saturation state, since the equilibrium is
      CaCO₃(aragonite) ⇌ Ca⁺⁺+CO₃⁻⁻.

      • Sure, Nick, carbonate becomes bicarbonate and pH is buffered, but within calcifying organisms, bicarbonate is transformed into carbonate, protons are pumped (and re-absorbed), aragonite and calcite are formed. Carbonate is not typically the raw ingredient for shell construction, rather, bicarbonate is.

        Furthermore, the mineral structure is covered by the periostracum, a protein layer that isolates the shell from the surrounding water and its hydronium ions. The shells of living organisms are not degraded as long as they are producing chitin.

        If we feel that there’s not enough carbonate in the ocean, how should we go about increasing it?

      • Nick,
        Le Chatelier’s Principle states that in an equilibrium reaction, adding more of one component of the equilibrium reaction will push the equilibrium away from the species being added.
        This is obvious.
        If a certain percentage of dissolved CO2 gas reacts with water to form carbonic acid, and a certain percentage of the carbonic acid dissociates into bicarbonate and hydronium ions, and a certain percentage of the bicarbonate dissociates into carbonate and hydronium (each of which percentages is extremely small as percentages go, but regardless), obviously more CO2 will result in more, not less, carbonate in solution as an ion.

        “Changing the concentration of a chemical will shift the equilibrium to the side that would reduce that change in concentration. The chemical system will attempt to partly oppose the change affected to the original state of equilibrium. In turn, the rate of reaction, extent, and yield of products will be altered corresponding to the impact on the system.
        This can be illustrated by the equilibrium of carbon monoxide and hydrogen gas, reacting to form methanol.
        CO + 2 H2 ⇌ CH3OH
        Suppose we were to increase the concentration of CO in the system. Using Le Chatelier’s principle, we can predict that the amount of methanol will increase, decreasing the total change in CO. If we are to add a species to the overall reaction, the reaction will favor the side opposing the addition of the species. Likewise, the subtraction of a species would cause the reaction to “fill the gap” and favor the side where the species was reduced.”

        Here is the equilibrium reaction of each of the species present when CO2 dissolves in water:

        H2O + CO2 ⇌ H2CO3 ⇌ H+ + HCO3– ⇌ H+ + CO3⁻⁻

        So obviously, when no interfering reactions are taking place (in seawater many other substances are present however), adding CO2 to the water will result in more carbonate.
        How could it be otherwise?
        And when carbonate is being removed by reacting with calcium ions to form calcium carbonate, it is necessarily the case that more bicarbonate will dissociate to oppose this removal.

        Now, plenty of alarmists have posited exactly the opposite, as you do here, on the theory that since adding more CO2 also makes more hydronium ions exist in the solution, and that this will react with the carbonate to form bicarbonate, so carbonate will decrease.
        But all of those species are in equilibrium prior to anything changing…except for the fact that other reactions are taking place simultaneously, and many of those are also equilibrium reactions, but some ARE NOT.
        Given only what you have stated though…you have it exactly backwards, unfortunately.
        People like Caldiera have been writing papers for years in which they postulate that adding CO2 to the oceans will result in less carbonate available and the result will be a decrease in such marine organisms as coccolithophores.
        But he uses obtuse reasoning and modelled results.
        The actual ocean says different, and more to the point, so do marine shell forming species such as coccolithophores…when they actually go look for them and do some counting!
        This is the sort of thing that happens when you get stuff backwards and never bother to check if what your models and poor understanding of how things work for real, is actually true.

        https://wattsupwiththat.com/2015/11/27/increased-carbon-dioxide-enhances-plankton-growth-opposite-of-what-was-expected/

        Also, if you kept up with current events, you would know that all of the alarmist predictions about the ocean are being found to be incorrect and that the opposite is happening.
        Shells are built of calcium carbonate, and to make that you need CO2.
        It is just like on land, when alarmist scientists claim that higher CO2 will cause us all to starve to death when our crops fail…but hey instead it turns out that since life is built out of CO2, more means more life, not less!
        Hooray…the end of the world is cancelled!
        Good night, drive safely, thanks for playing…you have plenty to live for it turns out, and being an alarmist is not one of them.

        • “Here is the equilibrium reaction of each of the species present when CO2 dissolves in water”
          But it isn’t dissolving in water. It is dissolving in seawater where a large amount of carbonate and bicarbonate is already present. Adding CO₂ does increase H⁺ (the pH does drop). So by Le Chatelier, in your last equilibrium, the change direction is that
          HCO₃⁻ ⇐ H⁺ + CO₃⁻⁻

          • Le Chatelier could not be expected to operate in any circumstance where there was not already the various ions in equilibrium.
            You want to ignore everything but the carbonate.
            The first thing that happens is more CO2 is added to the water.
            Then a little of it reacts with water to make carbonic acid.
            Then, due to the existing pH, this mostly is transformed into bicarbonate and Hydronium.
            But the solution is buffered, not just by bicarbonate.
            Ignoring that for this part of the sequence, more bicarbonate means there will be more carbonate, because there is more CO2!
            You cannot jump ahead and consider only the hydronium generated, and ignore that for every hydronium, there is also an additional ion of bicarbonate, which has a dissociation constant. This means that the two remain in a certain proportion relative to each other.
            Carbonate is only there because there is CO2 to begin with, but by your logic, the more CO2 you put in, the less carbonate there will be.
            That makes zero sense.
            Because you are not looking at the entire picture.
            And every time a calcium ion runs into an ion of carbonate, and/or they are absorbed, this is the other part of the principle…removing one species pulls the reaction towards the thing being taken away!
            The Ka values are calculated from actual solutions. More bicarbonate means there will be more carbonate. The H+ generated is part of the calculation.
            You cannot just pull them both over to one side!
            If what you are saying was true, adding CO2 would cause more bicarbonate to combine with acid and make still more CO2!
            This is exactly opposite of what happens.

          • Besides for everything else is the actual Earth.
            There are a large number of biomes where the pH is below 7, and yet shell fish live in vast profusions.
            Black smokers are highly acidic, and yet large numbers of various shelled organisms crowd around them.
            Cold waters in the Arctic and Antarctic have very low pH compared to lower latitudes, and yet these places have huge populations of all sorts of shelled organisms.
            Suwanee river and other so-called black water rivers have extremely low pH due to tannic acid and humid acid from decomposing leaves and such. Numerous freshwater mussels that live in these waters never got the memo that they could not live if the pH was low.
            And then there is all of Earth history, when CO2 was almost always many times higher than now.
            Neither chemistry or biophysics was different then.

          • ” but by your logic, the more CO2 you put in, the less carbonate there will be.
            That makes zero sense.”

            It’s just chemistry. The overall reaction is
            CO₃⁻⁻ + CO₂ + H₂O ⇌ 2HCO₃⁻
            Adding CO₂ pushes the reaction to the right – twice as many moles of HCO₃⁻, with the excess at the expense of CO₃⁻⁻.

          • The problem with pointing to simplistic atomic equations is that the real world clearly does not reflect the theoretical problem.
            Therefore the real problem is more complex, and the other effects are major or dominating, vs the “physics”.
            Then there’s the entire problem of the evolution of the genus Mollusca – it occurred in the Cambrian era where CO2 levels were in the 3000 ppm order.
            If Carbonate starvation due to CO2 levels is really such a problem, or pH, or whatever panicmongering “acidification” nonsense is true – these animals would never have evolved to start with.
            The ginormously thick shells of the early mollusks – cephalopod variety – argue that HCO3 = H+ + CO3 is not a serious issue.

          • For the two molecules, one the ionic carbonate and the other CO2, whether in solution or existing as the reaction product with water, carbonic acid, a certain proportionality exists.
            Part of the Ka and what causes it to vary as conditions vary is the fact that one of each have to collide in order to react.
            But for dissociation to occur, that is not the case.
            At a pH above 7, carbonic acid is immediately and almost totally dissociated. The reaction is reversible because the two dissociation products can collide and then combine again…the Ka is a small number when this is thermodynamically favored, and gets larger when the thermodynamics changes to make it less favorable.
            The predominant species at the pH of the ocean is bicarbonate…it is thermodynamically favored.
            When one examines the tables regarding what happens under various conditions, some certain temperature and CO2 partial pressure is specified, and yet under the ocean the temperature and the pressure are at far different and varying levels.
            The upshot is that it is extremely complex, which is why looking at some modelled result, even if the modeler had no inherent bias, must be compared to what is observed to occur in the actual ocean, in rivers, and lakes, near volcanic vents, etc.
            What is actually observed is increasing numbers of coccolithophores in the ocean, vast teeming profusion of shelled organisms including molluscs crowding around black smokers which are expelling hot concentrated brine loaded with CO2.
            Empirical evidence not gathered in ridiculous contrived aquarium tanks shows none of the effects predicted by alarmists, who have decided to rewrite whole textbook sections based on flawed reasoning, while tossing out and ignoring decades and centuries of accumulated knowledge and observations.
            And worst of all ignoring what we can observe to be occurring at the present time.
            Life evolved under real conditions, not calculated models, and has continued to evolve and prosper and survive as conditions have changed over time, in response to variations in the air above the ocean, the contents and conditions of the rivers dumping into the seas, the volcanoes and dep sea vents spewing and churning, upwelling of deep cold water of various mineral content…
            It is well known it has been far warner than now, even in the recent past, that sea level 18,000 years ago was hundreds of feet lower and therefore it is factual that over a period of thousands of years as the water rose, warmed, and increased in CO2 content, all of the reefs we see today that are above 400′ feet deep have grown from nothing to now exists.
            They survived the ice age and had no problem keeping up with huge changes in water level, salinity, temperature, pH, and CO2 concentration, over and over again…just in the recent geological past.
            Carbon dioxide is what life is built from…life in the water, and on land.
            It is only a political agenda that inspired the ideas now being promulgated by warmistas and alarmists of various stripe…the grifter, the opportunist, the politically power hungry, the control freaks, the gullible and credulous, the uneducated…

            If the theory does not agree with what is observed, the theory is wrong.
            It does not matter who says it, it does not matter how elegant it is.
            It is wrong.
            Period.

            https://wattsupwiththat.com/?s=ocean+acidification

          • “Therefore the real problem is more complex, and the other effects are major or dominating, vs the “physics”.”
            Physics, chemistry…these meet at a place called physical chemistry.
            Ask any medical school student or doctor what the hardest undergrad class they took was, and most of them will tell you P. Chem, without hesitation.
            These issues are where physical chemistry and biology intersect.
            What happens as things change introduces other factors relating to various other disciplines.
            It is impossible to separate what happens in the real world into separate disciplines and try to understand what happens while looking at only a small slice of reality, at some artificial division created in the minds of people.
            It all interrelates.
            Everything can and sometimes does affect everything else.
            By nothing occurs that does not accord with the physical laws of nature.
            How well people understand them and account for various factors, means that someone who thinks they can predict what will happen as something changes, can be and often is wrong.
            Besides for ignoring what is actually occurring, people bitten by the warmista bug have some sense that they cannot be wrong, that they do not need to be guided by what is observed, that if data contradicts what they have decided is the case…best to ignore it or change it or just make stuff up.
            We do not have to observe how these questions are argued by the same people who have shown themselves, in one area of science and argumentation after another, to be dishonest purveyors of junk science and propaganda and alarmism.

          • Nick, every time you make an assertion, you want to look at only on part of what is in reality a complex interactive series of equilibria.
            In the ocean, the buffering of numerous species means that pH changes very gradually, even with large changes in the concentration of CO2 and the weak acid it forms when combined with water.
            This means that whatever changes might take place as a result of changing pH, as described in the Bjerrum plot, are tiny compared to the changes forcing a new equilibrium with regard to Le Chatelier.
            It is inane sophistry to attempt to understand or explain one part of a chemical equilibrium without taking account of all of the reactions and equilibria which are affected as one or more change(s) occurs.

            Instead of honest investigation to resolve questions, the process has been short circuited by alarmist ideology.
            Conclusions are now assume.
            Questions are not honestly assessed, data is not objectively analyzed for purposes of verification.
            Anything that might contradict alarmist mentality and dispel warmista mythology are not even investigated.
            The mentality is exactly that which prevailed prior to the scientific revolution.
            Back in those days, very few of the things people thought they knew about the natural world were correct.

            “Phenomena in apparent contradiction to Le Chatelier’s principle can arise in systems of simultaneous equilibrium: see the article on the theory of response reactions. “

      • Stokes
        You said, “And so pH 7 is a canard too.” But it brings into focus that statements such as “becoming more acidic” are disingenuous, being unsupported by the facts or commonly accepted chemistry definitions.

  40. Willis,
    Excellent summary on ocean acidification.
    For general reading on the topic the following have excellent coverage and support your demolition of the feeble claims by the IPCC –
    1. “Climate: the Counter Consensus” ,pp 102-111 by the late Professor Robert M. Carter a marine biologist and Paleoclimatologist. This is the best short coverage I have read.
    2. “ Climate Change: The Facts”(2017), Ch. 2. ‘Ocean Acidification: Not yet a catastrophe for the Great Barrier Reef’ by Dr. John Abbott and Dr. Jennifer Marohasy.
    3.“Inconvenient Facts” by George Wrightson, Geologist. (Silver Crown 2017).
    Inconvenient Fact 55. There is no historic correlation between CO2 and Ocean pH.
    Inconvenient Fact 56.The oceans did not become acidic even with CO2 at 15 times modern levels.
    4. Ian Plimer “ Climate Change Delusion and the great Electricity Rip-off.”- Ocean Acidification pp326-341. Plimer has an excellent coverage as a geologist and calls ocean acidification a ‘concocted non- issue,”and
    “Mention of ocean acidification is a fraud.The oceans have been alkaline since the beginning if time (save very earliest oceans were probably acidic, Halevy 2017) and during times when the atmospheric CO2 was hundreds of times higher than now”.
    Lastly from Steve Goreham’s book-
    “Acid Oceans?
    Ocean acidification is a grand whopper that is frequently delivered by climate scientists,the IPCC, and environmental groups like the NRDC.
    … It is probably as difficult to develop a global average of ocean alkalinity as it is to develop a globalaverage surface temperature.
    The pH of the ocean varies by depth, becoming less basic as one goes deeper . It varies by latitude as one moves from the equator to the poles.It varies by location, such as open ocean, coral reef , or kelp bed. Scientists still know little about the alkalinity of today’s ocean or the oceans of past centuries.
    A December 2011 study by scientists at the Scripps Institution of Oceanography found large variations in ocean pH by month, week, and even time of day.Dr. Gretchen Hoffman led a team that measured pH at 15 locations in the Atlantic,Pacific and Antarctic oceans. They found that pH changes were large, from 0.1 to I.4 units over a 30 day-period. They also found that pH changed by as much as 0.35 units over a course of days!
    The study concluded that ‘ climatology based forecasts consistently under estimate natural variability’ and that ocean residents ‘are already experiencing pH regimes that are not predicted until 2100’ by the climate models.”
    The paper is Hoffman et al 2011.

  41. “…the web page containing the Monterey Bay pH dataset has become some kind of unknown Japanese web-page. Fortunately, I kept the data.”

    I see you’ve discovered the same thing I have, that the Internet changes too often for bookmarks to be useful. Whenever I find a good piece of information, I save it in PDF format, so I will always be able to go back to it later.

  42. Willis,
    Excellent overview in line with your body of work.
    I would only add that calcium in the form of CaCO3 is the other line used by the panic mongers to scare.
    And as far As I can see, there is no scarcity of Calcium in the ocean, period. In the southern ocean, because of the diatoms, there can be silicon scarcity but neither “dissolving” nor “insufficient calcium” is a teal thing.

    • There is over twice as much calcium ion in seawater as bicarbonate. Ca++ is usually given as about 400 ppm, and HCO₃⁻ as about 130-140 depending on the source.
      Carbonate ion is roughly as basic as hydroxide ion…they are adjacent on tables of bases listed by increasing strength.
      What this means is that there is very little of it to begin with, compared to other species it is in equilibrium with.
      This is reflected in tiny Ka values for it’s conjugate acids.
      4.7 x 10⁻¹¹ is the Ka of bicarbonate.
      Carbonate is present in amounts so small it is typically disregarded in equations, and does not appear on most charts of the ions present in sea water.
      One can find many assertions that carbonate is present at about 1/10th of the concentration of bicarbonate, but list after list from references do not even show it. Even ones that list major and minor components. I do not knw what is up with that…but the tables comport with what one might expect, and do not agree with assertions of as much as 14 ppm of carbonate.

      https://chem.libretexts.org/Courses/University_of_Arkansas_Little_Rock/Chem_1403%3A_General_Chemistry_2/Text/16%3A_Acids_and_Bases/16.3%3A_Equilibrium_Constants_for_Acids_and_Bases

      Ok, here is one reference.
      A graph from GSU.
      https://cpb-us-w2.wpmucdn.com/sites.gsu.edu/dist/0/134/files/2013/02/pHcarbonate_1989-2010.png

      sites.gsu.edu/geog1112/carbon-cycle-day-2-part-5/

      228 micromoles per kilogram. 60 grams per mole is molecular weight, so that is about 13 milligrams per kilogram. Which if I am looking at this right is about one tenth of the bicarbonate concentration. So I wonder why none of the usual reference tables list it?
      Is does not say if this is a measured or calculated result, although it would be worthless to just calculate it.

  43. Forget the carbonic acid as EVs won’t save poor Nemo-
    “This is dust and particulates that are emitted from our tyres constantly – and our brakes when we use them. This currently unregulated source of pollution contributes to particulates in the air, as well as microplastics in the ocean.”
    https://www.msn.com/en-au/motoring/research/tyre-emissions-1000-times-worse-than-exhausts/ar-BBZvfoU
    They’re gunna have to slash the weight of those EV batteries to comply with the new Regs for this dire threat to Gaia.

    • EV’s typically use regenerative braking, charging batteries as they do, when they brake so less wear on braking systems. EV’s typically have harder compound tyres too to reduce rolling resistance. But yeah, curb weight of a Tesla 3 is 1.9 tonnest give or take a few KGs. That’s a big vehicle to handle if not used to that mass. There will be some wear regardless.

  44. Willis, I don’t know where your pH graphic originated but I’ll be concluding my day soaped down in the shower, though thereby fortunately not at all exposed to anything close to the alkalinity of the very lye used (and chemically defanged) in the making the soap from animal fats! Also sodium hypochlorite bleach is classically produced by passing chlorine gas through a lye (sodium hydroxide) solution, so the resulting pH is from the latter and not then neutralized with acid because that would destabilize the solution with chlorine gas release.

  45. Consider the following restatement of their opening sentence.

    “The Pacific Ocean is becoming so less caustic it is starting to dissolve the shells of a key species of crab, according to a new US study.”

    The absurdity of “OA” language is made apparent when you consider that calling something acidic, that is on the alkaline side of neutral, is the equivalent of calling any substance on the acid side of neutral, caustic!

    To restate, if you dilute an acid*, is it better described as (a) less acidic or (b) more caustic? /rhetorical

    The stupid, it really burns! 😉

  46. One less known facts about Ph neutrality is that it depends on temperature.

    Pure water only has Ph 7 when the temperature is 25 Celsius. At 0 Celsius the Ph is 7.47 and at 100 Celsius the Ph of pure water is 6.14.

    However, pure water is akways neutral, which means that Ph neutal at 0 Celsius is 7.47.

    /Jan

  47. Willis, thank you once again for your contributions.

    An interesting analysis of the effects of pH on oceans might be found from studying the mouth of tha Amazon. B i g river. Lots of water. From what I have gleaned, its waters really are acidic. So what does the immediate area of the Alantic look like wrt fishing and coral reefs? Well, I won’t spoil the ending, but it is clear that the primary thing to consider are the nutrients flowing into the ocean. pH? Not so much.

  48. Lately I found some 15 cm big Swan mussels some 20 kilometer from where I live. For info about swan mussels: https://en.wikipedia.org/wiki/Swan_mussel

    They live in fresh water. The ones I’ve found came from a very peaty environment, well known for its high acidity. Birds supposedly deposited the shells 3 meter from the fresh water pool on surrounding peaty soil. In the water some floating peat was visible, I think the birds took the shells from peat that sometimes rises up from the bottom of the pool of water as methane gases make some bottom-peat float.

    According to this source https://umaine.edu/oronobogwalk/wp-content/uploads/sites/393/2015/03/Peatland-Acidification-pH.pdf the peaty soils described in this paper show a pH “ranging from about 6.6 to 3.6”.

    The shells of my freshwater peat swan mussels looked perfect: very hard. Some examples of comparable swan mussels in the middle of this link: http://www.natuur-natuurlijk.nl/de-wondere-wereld-van-de-zwanenmossel/

  49. OK. Has anyone sat down and calculated what the effect on pH would be if all of the earth’s atmospheric CO₂ was dissolved into the ocean? I mean every last molecule of CO₂. It seems rather strange to me that the mass present in ~400 ppm atmospheric content could cause much if any change to the pH of the much more massive ocean.

    Anyone? My university chemistry talents have long evaporated.

    • Mike, such a calculation would be meaningless for two reasons.

      First, most of the Earth’s carbon is stored in fossil sediments, just a tiny fraction is in the atmosphere. A more meaningful calculation would be to calculate how the Ph in the sea will develop if we continue to burn fossil fuel in increasing amount each year, and half of it continue to dissolve in the sea.

      Secondly, the Ph of the entire ocean is not changing much, we see a noticeable effect only in the surface water.

      /Jan

      • Jan kjetil Andersen February 1, 2020 at 11:21 pm

        A more meaningful calculation would be to calculate how the Ph in the sea will develop if we continue to burn fossil fuel in increasing amount each year, and half of it continue to dissolve in the sea.

        Jan, that’s the number I quoted and showed in the graphs, 0.08 pH units by the year 2100 assuming the RCP 6.0.

        w.

        • Oh, I did not notice that.

          Excellent article, although it is worth mentioning that a change from alcalic environment to more Ph neutral environment can have a negative impact on some of the flora and fauna that are used to the alcalic environment.

          /Jan

  50. Willis posted in the original post But at a couple of hundred metres under the surface off the coast of Alaska (top right), the ocean is at a pH of 7.25. This pH is what hysterical scientists and the Guardian would call “MUCH MORE ACIDIC!!”, but is properly called “approaching neutral”.

    Actually at a temperature of 10ºC a pH of 7.25 is acidic (just). Neutrality is at pH 7.0 only at 25ºC.

    • Phil, that’s true, but only in pure water at surface pressure. Seawater is an entirely different beast. And generally, and for the reasons you state, in ocean studies the in-situ measured pH is converted to a standard temperature etc before being reported.

      I use the R package “seacarb” for this kind of calculation. Here’s a typical function:

      pH at in situ temperature and pressure
      Description
      pH at in situ temperature and pressure
      
      Usage
      pHinsi(pH=8.2, ALK=2.4e-3, Tinsi=20, Tlab=25, Pinsi=0, S=35, Pt=0, Sit=0, 
        k1k2 = "x", kf = "x", ks="d", pHscale = "T", b="u74", eos = "eos80", 
        long = 1e+20, lat = 1e+20)
      Arguments
      pH	
      pH measured in the laboratory
      
      ALK	
      ALK, total alkalinity (mol/kg)
      
      Tinsi	
      In situ temperature in degrees Celsius
      
      Tlab	
      Measurement temperature in degrees Celsius
      
      Pinsi	
      In situ hydrostatic pressure in bar (surface = 0)
      
      S	
      Salinity
      
      Pt	
      value of the concentration of total phosphate in mol/kg
      
      Sit	
      the value of the total silicate in mol/kg
      
      k1k2	
      "l" for using K1 and K2 from Lueker et al. (2000), "m06" from Millero et al. (2006), "m10" from Millero (2010), "w14" from Waters et al. (2014), and "r" from Roy et al. (1993). "x" is the default flag; the default value is then "l", except if T is outside the range 2 to 35oC and/or S is outside the range 19 to 43. In these cases, the default value is "w14".
      
      kf	
      "pf" for using Kf from Perez and Fraga (1987) and "dg" for using Kf from Dickson and Riley (1979 in Dickson and Goyet, 1994). "x" is the default flag; the default value is then "pf", except if T is outside the range 9 to 33oC and/or S is outside the range 10 to 40. In these cases, the default is "dg".
      
      ks	
      "d" for using Ks from Dickon (1990), "k" for using Ks from Khoo et al. (1977), default is "d"
      
      pHscale	
      choice of pH scale: "T" for the total scale, "F" for the free scale and "SWS" for using the seawater scale, default is "T" (total scale)
      
      b	
      "l10" for computing boron total from the Lee et al. (2010) formulation or "u74" for using the Uppstrom (1974) formulation, default is "u74"
      
      eos	
      "teos10" to specify T and S according to Thermodynamic Equation Of Seawater - 2010 (TEOS-10); "eos80" to specify T and S according to EOS-80.

      Assuming a difference in pressure and temperature but with other parameters (salinity etc) the same, I find:

      pHinsi(pH=7,Tinsi=10,Pinsi = 10)

      [1] 7.16

      This says that neutral in the laboratory is a pH of 7.16 at a temperature of 10°C and a pressure of 10 bar.

      Regards,

      w.

  51. “The Strait of Juan De Fuca is the blue channel leading into the land. Seattle and Tacoma, Washington are below the inner end of the Strait. Vancouver Island, Canada, is on the north side of the Strait.

    It appears that the buoy is brought in when the weather gets very rough, because there is a gap in the data each winter.”
    ____________________________________

    Willis, seems there’s more than 1 buoy at La Push, in the Strait of Juan De Fuca:

    https://www.pmel.noaa.gov/co2/story/La+Push

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