Guest Post by Willis Eschenbach
There’s an interesting study out on the natural pH changes in the ocean. I discussed some of these pH changes a year ago in my post “The Electric Oceanic Acid Test“. Before getting to the new study, let me say a couple of things about pH.
The pH scale measures from zero to fourteen. Seven is neutral, because it is the pH of pure water. Below seven is acidic. Above seven is basic. This is somewhat inaccurately but commonly called “alkaline”. Milk is slightly acidic. Baking soda is slightly basic (alkaline).
Figure 1. pH scale, along with some examples.
The first thing of note regarding pH is that alkalinity is harder on living things than is acidity. Both are corrosive of living tissue, but alkalinity has a stronger effect. It seems counterintuitive, but it’s true. For example, almost all of our foods are acidic. We eat things with a pH of 2, five units below the neutral reading of 7 … but nothing with a corresponding pH of 12, five units above neutral. The most alkaline foods are eggs (pH up to 8) and dates and crackers (pH up to 8.5). Heck, our stomach acid has a pH of 1.5 to 3.0, and our bodies don’t mind that at all … but don’t try to drink Drano, the lye will destroy your stomach.
That’s why when you want to get rid of an inconvenient body, you put lye on it, not acid. It’s also why ocean fish often have a thick mucus layer over their skin, inter alia to protect them from the alkalinity. Acidity is no problem for life compared to alkalinity.
Next, a question of terminology. When a base is combined with an acid, for example putting baking soda on spilled car battery acid, that is called “neutralizing” the acid. This is because it is moving towards neutral. Yes, it increases the pH, but despite that, it is called “neutralizing”, not “alkalizing”.
This same terminology is used when measuring pH. In a process called “titration”, you measure how much acid it takes to neutralize an unknown basic solution. If you add too much acid, the pH drops below 7.0 and the mixture becomes acidic. Add too little acid, and the mixture remains basic. Your goal in titration is to add just enough acid to neutralize the basic solution. Then you can tell how alkaline it was, by the amount of acid that it took to neutralize the basic solution.
Similarly, when rainwater (slightly acidic) falls on the ocean (slightly basic), it has a neutralizing effect on the slightly alkaline ocean. Rainwater slightly decreases the pH of the ocean. Despite that, we don’t normally say that rainwater is “acidifying” the ocean. Instead, because it is moving the ocean towards neutral, we say it is neutralizing the ocean.
The problem with using the term “acidify” for what rainwater does to the ocean is that people misunderstand what is happening. Sure, a hard-core scientist hearing “acidify” might think “decreasing pH”. But most people think “Ooooh, acid, bad, burns the skin.” It leads people to say things like the following gem that I came across yesterday:
Rapid increases in CO2 (such as today) overload the system, causing surface waters to become corrosive.
In reality, it’s quite the opposite. The increase in CO2 is making the ocean, not more corrosive, but more neutral. Since both alkalinity and acidity corrode things, the truth is that rainwater (or more CO2) will make the ocean slightly less corrosive, by marginally neutralizing its slight alkalinity. That is the problem with the term “acidify”, and it is why I use and insist on the more accurate term “neutralize”. Using “acidify”, is both alarmist and incorrect. The ocean is not getting acidified by additional CO2. It is getting neutralized by additional CO2.
With that as prologue, let me go on to discuss the paper on oceanic pH.
The paper is called “High-Frequency Dynamics of Ocean pH: A Multi-Ecosystem Comparison” (hereinafter pH2011). As the name suggests, they took a look at the actual variations of pH in a host of different parts of the ocean. They show 30-day “snapshots” of a variety of ecosystems. The authors comment:
These biome-specific pH signatures disclose current levels of exposure to both high and low dissolved CO2, often demonstrating that resident organisms are already experiencing pH regimes that are not predicted until 2100.
First, they show the 30-day snapshot of both the open ocean and a deepwater open ocean reef:
Figure 2. Continuous 30-day pH measurements of open ocean and deepwater reef. Bottom axis shows days. Vertical bar shows the amount of the possible pH change by 2100, as estimated in the pH2011 study.
I note that even in the open ocean, the pH is not constant, but varies by a bit over the thirty days. These changes are quite short, and are likely related to rainfall events during the month. As mentioned above, these slightly (and temporarily) neutralize the ocean surface, and over time mix in to the lower waters. Over Kingman reef, there are longer lasting small swings.
Compare the two regions shown in Fig. 1 to some other coral reef “snapshots” of thirty days worth of continuous pH measurements.
Figure 3. Thirty day “snapshots” of the variation in pH at two tropical coral reefs. Bottom axis shows days.
There are a couple of things of note in Figure 3. First, day-to-night variations in pH are from the CO2 that is produced by the reef life as a whole. Also, day-to-night swings on the Palmyra reef terrace are about a quarter of a pH unit … which is about 60% more than the projected change from CO2 by the year 2100.
Moving on, we have the situation in a couple of upwelling areas off of the California coast:
Figure 4. Thirty day pH records of areas of oceanic upwelling. This upwelling occurs, among other places, along the western shores of the continents.
Here we see even greater swings of pH, much larger than the possible predicted change from CO2. Remember that this is only over the period of a month, so there will likely be an annual component to the variation as well.
Figure 5 shows what is going on in kelp forests.
Figure 5. pH records in kelp forests
Again we see a variety of swings of pH, both long- and short-term. Inshore, we find even larger swings, as shown in Figure 6.
Figure 6. Two pH records from a near-shore and an estuarine oceanic environment.
Again we see large pH changes in a very short period of time, both in the estuary and the near-shore area.
My conclusions from all of this?
First, there are a number of places in the ocean where the pH swings are both rapid and large. The life in those parts of the ocean doesn’t seem to be bothered by either the size or the speed these swings.
Second, the size of the possible pH change by 2100 is not large compared to the natural swings.
Third, due to a host of buffering mechanisms in the ocean, the possible pH change by 2100 may be smaller, but is unlikely to be larger, than the forecast estimate shown above.
Fourth, I would be very surprised if we’re still burning much fossil fuel ninety years from now. Possible, but doubtful in my book. So from this effect as well, the change in oceanic pH may well be less than shown above.
Fifth, as the authors commented, some parts of the ocean are already experiencing conditions that were not forecast to arrive until 2100 … and are doing so with no ill effects.
As a result, I’m not particularly concerned about a small change in oceanic pH from the change in atmospheric CO2. The ocean will adapt, some creatures’ ranges will change a bit, some species will be slightly advantaged and others slightly disadvantaged. But CO2 has been high before this. Overall, making the ocean slightly more neutral will likely be beneficial to life, which doesn’t like alkalinity but doesn’t mind acidity at all.
Finally, let me say that I love scientific studies like this, that actually use real observations rather than depending on theory and models. For some time now I’ve been pointing out that oceanic pH is not constant … but until this study I didn’t realize how variable it actually is. It is a measure of the “ivory tower” nature of much of climate science that the hysteria about so-called “acidification” has been going on for so long without an actual look at the actual ocean to see what difference a small change towards neutrality might actually make.
My best regards to everyone,
w.
NOTE: For those hard-core scientists that still want to call adding a small amount of acid to a basic solution “acidifying” the basic solution, and who claim that is the only correct “scientific terminology”, I recommend that you look at and adopt the scientific terminology from titration. That’s the terminology used when actually measuring pH in the lab. In that terminology, when you move towards neutral (pH 7), it’s called “neutralization”.
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“Figure 4. Thirty day pH records of areas of oceanic upwelling. This upwelling occurs, among other places, along the eastern shores of the continents. ” I had thought the upwelling more characteristic of the eastern shores of the oceans, as off Peru – but perhaps that’s what you meant. Interesting article anyway, Willis. For those who want to read more on this subject, there’s a popular scientific website with a regularly updated archive of research on the biological effects of slightly lowered oceanic pH. It seems the effects can be beneficial.
[Indeed, on the western side of the continents is correct, my error. I’ll fix it. Thanks. —w.]
ferd berple says: December 28, 2011 at 12:42 am
………In moist environments steel rusts much quicker when there is high levels of CO2 from cities and industries for example, than in rural areas.
*************************
Hmmmmmm………Reference??
Puzzled and Bewildered,
Steamboat Jack (Jon Jewett’s evil twin)
Somewhat off topic, but the World needs to konw what passess for educational “debate” in the UK.
http://www.decc.gov.uk/assets/decc/11/tackling-climate-change/2050/3670-2050-schools-toolkit-pdf-version.pdf
I really do think a legal challenge to this sort of Government produced AGW propaganda masquerading as teaching materials is long overdue.
Acidified, neutralized, or whatever, it doesn’t matter that much in the grand scheme of things. Simply because nature will adapt, compromise, evolve, or whatever. Humans will, being part of nature, get moved along with the Great Slurry.
I’m in agreement with Willis, that the intent of the language is alarmist. The effect of the process is marginal and life will adapt. Given that anthropogenic CO2 emissions are but 4% of the total, It’s hard for me to accept serious responsibility for the “acidification”.
Besides, there are creatures that thrive in acidic environments, like acidithiobacillus ferrooxidans, and some will even make their own acid if needed. Species adapt, and to believe the oceans have always been at a constant pH is patently absurd.
Yeah one of the things that geologists rile over is that the full oceanic conditions, including oceanic volcanoes, Mid Oceanic Ridges (expelling and intaking enormous amounts of seawater and exchanging chemicals), the processes and rate of non-organic carbonate precipitation and dissolution within seawater, etc etc cannot be easily reproduced in the laboratory. It is highly likely, that the oceans are strongly buffered, for a variety of reasons, against even modest scale pH changes,which, as usual is not incorporated in the alarmist models.
Even wikipeadia mentions that carbonate dissolution and precipitation, which is in an equilibrium state strongly sensitive to any changes in ocean chemistry, on the sea floor is likley to mitigate the effects of long term oceanic intake of c02 and climate change, but they carefully state that this effect is only likely to be significant over time scales of centuries. I am not so sure, chemical dissolution and precipitation effects are is more or less instantaneous.
From wikipedia:
“Leaving aside direct biological effects, it is expected that ocean acidification in the future will lead to a significant decrease in the burial of carbonate sediments for several centuries, and even the dissolution of existing carbonate sediments.[53] This will cause an elevation of ocean alkalinity, leading to the enhancement of the ocean as a reservoir for CO2 with moderate (and potentially beneficial) implications for climate change as more CO2 leaves the atmosphere for the ocean.”
I have drilled through thousands of metres of carbonate- enriched sediments and volcanics, from undersea volcanoes, which interact with ocean chemistry in the subsurface of the oceans on a worldwide, and very large, scale. Changes in carbonate chemistry in the ocean will directly effect the dissolution and precipitation rates of carbonate within these large volumes of sediments around these massive heat sources-which extend for thousands of kilometres in every ocean (eg Mid Oceanic Ridges). I have never seen one paper discuss or address this.
Willis, you are right to complain about inaccurate language, language that sounds scary to average people. Climate change activists and their syncophants (e.g., “reporters”) want to keep up the barrage of scare stories.
But there are potential issues behind the scary headlines. The issue is the extent to which lower pH in the ocean affects the carbonate cycle of creatures that build shells — will they dissolve, or more likely, will it be hard for creatures to build shells with lower pH. You have probably seen the scary video of a carbonate plastic bottle slowly dissolving, disappearing, as the pH is slightly lowered. That is part of the scary story hype as well.
Scientists are actually doing real world experiments now, and are finding that most creatures that build shells or carapaces — crabs, oysters, corals, clams, urchins, and so on — actually can continue to build shell at lower pH than most had previously thought, without much drop in the pace of shell or coral building. If we were to get to atmospheric CO2 of around 1,500 ppm (we are very far from that), then my read of the science is that some creatures would have difficulty building shell (some oysters, for example) but others would not (lobsters, for example, which continue to build more shell, even when CO2 levels are above 2,700 ppm).
So there is a legitimate issue, albeit one that is overhyped as usual, when CO2 gets very high and pH below 7.5 or so, for some creatures. Whether there is an issue at 700 ppm or 900 ppm appears unlikely for many shell builders, according to the science that has been done so far, but there could yet be an issue for some. Therefore: we actually need to do science. Some people are actually doing that, and discovering that in most cases, slightly lower pH, the levels associated with 600 or 700 ppm CO2, don’t get in the way of shell building, or coral reef building, and so on. But I would agree that we need to keep doing the science.
None of the above in any way disputes your point about once again the warmists are telling scare stories. I’m waiting for the one about polar bears dissolving on their long swims when there is no ice…..
I find no shortage of amazement at the effort humans will place on self-deception for the purpose of preserving a cherished fear.
In general, animal cells, including fish cells, can better withstand a one unit drop in pH from their normal value than a one unit increase.That is why we use a pH incidator in mammalian cell culture where 7.4 is the set value (like blood). Orange (pH 6) is still OK, purple (pH 8.5) is byebye. Thus it is true that acidification is better tolerated than alcalination. However, we do talk of acidification when the pH decreases from its set value. So while talking of “acidification of the ocean” may be intentionally misleading it is scientifically correct.
Pamela Gray…
What is the quote from Thomas Jefferson… “A little revolution, every now and then, is a good thing”
The dire consequences of ocean acidification is one of the most ridiculous claims made by Globalwarmists. Atmospheric CO2 was more than 10 times higher during the nearly all of the Paleozoic compared to today. Somehow, corals and other creatures with calcite shells and skeletons survived just fine and managed to form gigantic reefs visible in many places in the world. They didn’t dissolve. Yet, somehow, this concept is incomprehensible to the alarmist crowd.
I’ve had arguments about ocean water “acidification” a number of times. In particular, there was an unnamed clown who sincerely believed that reduction of the ocean’s pH from 8.2 to 7.8 would rapidly dissolve calcium carbonate animal shells. Clearly, he didn’t understand chemistry at all. To demonstrate, I put a nice, fresh sea shell into a jar of distilled water and put it right where he could see it for about six months. Even at the frighteningly acidified pH of 7.0, the shell didn’t change.
His response? “Proves nothing. The experts know what they’re talking about. You’re just a geologist.”
Too bad I don’t work there anymore. I’d love to see his reaction when he found out I’m now an official “IPCC Expert Reviewer”.
Steve Keohane says:
December 28, 2011 at 6:29 am
“Maybe I’m wrong, but I thought an excess of H ions was acidic, an excess of OH ions alkaline, and you have one or the other. An alkaline solution doesn’t become acidified until there are no OH ions, when pH7) takes the hydrogen ion concentration back to the level present in pure water, not to zero.
So, back to the semantical question: In my view, absent the “alarmist’s” capture of the therm “acidification”, it is a perfectly acceptable term as it accurately desribes the direction of measurement, i.e., to a greater concentration of hydrogen ions. If not narrowly defined, “neutralization” suggests movement to a state of NO hydrogen ions, which is objectively incorrect.
I’ve always been amused by some of the health nut quackery about avoiding “acidifying” the body. It is interesting how people get their misconceptions and how they translate across sectors. They see acid in movies and so they are afraid of acid in the body and the oceans.
They see that the sun powers the mighty Superman and so they assume solar power has great potential.
However, I must take exception to the most basic food being dates. I’m not positive, but I think century eggs might be more basic. The preservation process uses lye.
Maybe that’s why they taste so…..odd.
Steve Keohane says:
December 28, 2011 at 6:29 am
In pure water, a small percentage of molecules break into ions, and winds up at 10^-7 molar concentrations of both H+ and OH-. The negative of the log of H+ is pH, i.e. -log(10^-7) = 7.
In an acidic solution, there’s a lot more H+ kicking around, so the pH is lower. They also scavenge the OH-, so there’s a lot less of them. In a basic solution, there’s an excess of OH- and they scavenge H+, so the pH is higher. I think? learned? assumed? that the sum of the logs of each concentration was always -14. At least equal amounts of pH 4 and pH 10 solutions leave a neutral solution, discounting effects of buffering, precipitation, and other reactions.
“I like pickled beets but not biscuits with too much baking soda.”
I sure hope you mean baking powder.
mkelly says:
December 28, 2011 at 6:38 am
JJ we are talking about the oceans or did you miss that.
My post was to Willis, and he was talking about a lot more than just oceans. He was talking about food and human stomachs and all manner of other things, and pretending that those had relevance to the oceans. They do not. That was my point, or did you miss that?
So your sentence above is what he was talking about. ie.
Absolutely false.
The life in the oceans are not harmed by the small variation caused by a change in pH from CO2 because they started there.
That assertion is not supported by anything that Willis posted. Biochemistry is a very complex subject, and cannot be truthfully replaced with platitudes like “Life doesn’t like alkalinity, but doesn’t mind acidity at all.” That statement is not true, and complex subjects like biochemistry cannot be simplified by mixing well with equal parts bullshit. Willis needs to learn that, and having done so he can move on to learning the difference between acute and chronic toxicity. That bit invalidates the rest of Willis’ post.
I like pickled beets but not biscuits with too much baking soda.
We pickle beets, cucumbers, and other vegetables with acid. We do that to keep other living organisms from eating our food. Acid kills those living organisms. See, even you can come up with common sense disproofs of the silly statement that “life doesn’t mind acidity at all” – and you weren’t even trying.
“Declining”??? “Increasing”??
In using [and debating]m these terms, please remember that pH is minus [negative] the log of the hydrogen ion activity [concentration] so that, among other things, that cute little scale at the left of Willis’ diagrams is logarithmic.
Thanks for this post, Willis.
You say:
“It is a measure of the “ivory tower” nature of much of climate science that the hysteria about so-called “acidification” has been going on for so long without an actual look at the actual ocean to see what difference a small change towards neutrality might actually make.”
The reason why the ivory tower inhabitants use ‘acidification’ is of course the thorough politicisation of climate science.
No NGO or propagandist worthy of their name would use such un-scary expressions as ‘neutralisation’, when they can scare normal people with ‘acidic’ and, see your quote above, even ‘corrosive’.
It is the same process which mutated CO2 into ‘carbon’ – a black, dirty, stuff.
Both these expressions link to fear (corrosive) and pollution (carbon) in the mind of the ordinary people. It is a technique used by advertising agencies, and any woman who has ever watched a TV commercial about washing powder washing whiter than white will unconsciously agree that this dirty black stuff carbon ought to be forbidden.
It is political propaganda all the way down …
Willis, thank you, again!
I’m glad I’m a realist, as if that were not the case I would be at a loss to try to debunk you.
You sir, have an overall knowledge base that is incredible. Your presentations of the facts / science is overwhelmingly conductive to communication.
Carry on!
BUFFERING: Willis, perhaps you or another more expert than I can comment on the buffering effect of the ocean water, a subject so far not discussed (or perhaps unknown) within the simplists’ view of acidification….. As we know ocean water is salty consisting of ionized form of sulfates, chlorides and the like. Given its volume and concentration of these salts makes ocean water the most gigantically-potent buffer known. Since the effect of a buffer is to block or impede any change in pH, is my thinking correct to say that the effect of any addition of carbon dioxide, or alkaline or acidic compound would be “blocked” or “neutralized” by the buffering effects of worlds’ oceans?
JJ says:
December 28, 2011 at 8:41 am
mkelly says:
December 28, 2011 at 6:38 am
JJ we are talking about the oceans or did you miss that.
JJ says : “Absolutely false.”
“The Ocean Is Not Getting Acidified” title of post.
I believe JJ you are wrong again. See title of post above.
Again, you miss the point I eat pickled beets (acid) and they do me no harm and I enjoy them. The base (baking soda) loaded biscuits I cannot eat under any circumstances.
Don K says:
December 28, 2011 at 2:43 am
Thanks, Don. In the world of how we actually use language, your distinction is not true. As I pointed out, we put baking soda on spilled battery acid to neutralize it, and the “ph of the medium” is about 1, well below 7. In English, “neutralize” means to make neutral or to move in the direction of neutrality regardless of the pH of the medium.
w.
I see Dr Rogers corrected the pH definition to activity not concentration. Something I’ll never forget after getting a face to face lecture on it from the fellow running the Freshman Chem Lab.
Also there is a practical reason for using acids as the titrant (material used to titrate unknown solutions). Basic (aka alkaline) solutions absorb CO2 from the air and change their pH. Acid solutions don’t and are easier to store and to keep at a known concentration. So acid solutions are preferentially used.
The fellow who thinks CO2 accelerates metal corrosion in alkaline solutions is wrong. CO2 react with water to form -HCO3 + H+, the H+ will neutralize alkaline solution but will acidify neutral or acid solutions. The increased acidity in acid solutions might accelerate corrosion. But a high pH solution with very high carbonate (sodium carbonate solution for example) will be protective of iron. Indeed this has a name, it is called passifying the metal surface.
Willis’s chart on the reef is a good example demonstrating CO2 is not a major issue with respect to shallow water pH – reefs or other any other shallow habitat. There are simply too many other potential processes at work including the sediment-water column sulfur cycle (ex. H2S) , nitrification/de-nitrication alkalinity effects, terrestrial organic acid inputs, photosynthetic response, respiration that overwhelm the rather small impact of a small change in pCO2. And if this were not sufficient to make the point- these shallow water marine habitats are also subject to the chemistries/dilution of the groundwater flux moving up through the sediments and/or the more direct inputs of surface freshwater sources.
Yet most of the papers touting the dangers of “ocean acidification” utilize the inhabitants of these shallow habitats to justify the alarm.
Although I’m not so sure I would ascribe to alkaline being any worse (or better) than acidic as this post does. They’re just different states with different eco-systems organizing/adapting around it. What is seen is as good and bad is generally nothing more than a value judgement.
SOLUBILITY OF CARBON DIOXIDE–>FORMATION OF LIMESTONE: Willis, there is an other topic of concern so far lacking in any discussion of CO2 in worlds oceans. Perhaps someone more knowledgeable could comment on this. It is the CO2 balance between that of cold and warm waters. (Search Internet for CO2 Solubility Curve.) That is what happens between CO2 and sea water in the Arctic/Antarctic versus CO2 and water in the tropics. Inherent in this topic is the vastly increased solubility, or so the chemists say, of CO2 in cold water of up to 3.5 g/kg water compared to only 0.5 g/kg water for water at tropical temperatures. From this we can conclude that CO2 is many times more soluble in cold compared to tropical waters. Less well known is that the upwelling of CO2-oversaturated waters in the tropics is likened to a “failsafe” mechanism that opposes overproduction of CO2 leading to the transfer of CO2 to limestone. This action results in a release of CO2 leading to precipitation of limestone. As cold waters move from depth toward the surface in the tropics, become CO2-oversaturated, and in the presence of calcium and bicarbonate ions, precipitate as calcium carbonate, limestone, in many forms: by action of shelled organisms, for coralline structures, as carbonate muds (i.e. Andros Is.), as oolite, pisolites, algal heads, and many other forms of precipitates. The overall effect is a moderation or a reduction of the oversaturated state of CO2. Geologists know that mountain ranges across the US, Canada, Europe, Asia are built mainly of limestone. Limestone deposits have formed on earth’s crust since early Precambrian time. Limestone is the final product of this natural failsafe mechanism.
DocWat says:
December 28, 2011 at 7:36 am
Pamela Gray…
What is the quote from Thomas Jefferson… “A little revolution, every now and then, is a good thing”
‘The tree of liberty needs to be watered with the blood of tyrants and patriots every 25 years’ is closer to what he said per my old person’s memory.