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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Viv Evans,
Agreed we are talking about the ability to osmoregulate that allows some fish to move back and forth between fresh and salt water environs. However there is one that is impacted by pH- the Atlantic Salmon that experiences high mortality on its initial voyage to the ocean at a pH much below 6.5. I’m not sure that I know of any other anadromous or catadromous species with this tight pH restriction. (And no this has nothing to do with CO2 driven acidification)
@ur momisugly Pat Moffitt, December 28, 2011 at 12:54 pm:
No, I can’t think of any other species than the Atlantic salmon either.
And yes – osmoregulation has nothing to do with CO2.
I just got cross because, in ivory-tower fashion, that ‘John of the West’ seemed to imagine that there’s this fixed boundary between fresh water and sea water, which fish and other animals can only cross at pain of death.
That’s what happens when people sit in front of their PCs, pontificating, but can’t get their wellies on and take a nice long trip up and down the local beaches, river mouths included, to see what is actually going on.
Adapted from the Wiki-bloody-pedia:
“The Messinian Salinity Crisis, refers to when the Mediterranean Sea went into a cycle of partly or nearly complete desiccation in the latter part of the Messinian age of the Miocene epoch, from 5.96 to 5.33 Ma. It ended with the so-called Zanclean flood, when the Atlantic reclaimed the basin. The water from the Mediterranean would have been redistributed in the world ocean, raising global sea level by as much as 10 meters. The Mediterranean basin also sequestered below its seabed a significant percentage of the salt from Earth’s oceans; this decreased the average salinity of the world ocean and raised its freezing point.”
So, how did marine life outside the Mediterranean basin cope with these massive changes in salinity and presumably pH? Can’t seem to find much change myself.
It’s a strange crusade you’re on, to try to make out that acidification cannot be a bad thing. And you’re trying to claim that ocean acidification is not a problem because fruits are acidic and not alkaline? And because humans eat things further below seven than above seven on the pH scale? This is magnificently unconvincing, and you clearly don’t even appreciate that the concept of “neutral” is simply an arbitrary point on an arbitrary scale.
Pat Moffitt says:
December 28, 2011 at 12:54 pm
“However there is one that is impacted by pH- the Atlantic Salmon that experiences high mortality on its initial voyage to the ocean at a pH much below 6.5.”
Where exactly are they encountering pH values below 6.5 in the world’s oceans?
There is a major problem in this analysis that is being overlooked and ignored. Yes, there are deviations from the short-term average that occur in these locations shown above. Consider them high frequency noise. Most items that interact in a system will occasionally experience deviations outside the normal. It is to be expected. Consider the “normal” distribution. Most of the time we expect to find the result in a particular range, but we can experience deviations outside of this normal, but these events are unusual and not long lasting.
The problem is when the average is constantly lower, not just for a short period of time. If there is a large rainfall, the local sea-surface salininty may go down sharply (don’t want to fight which way the pH may go). But it will return to normal salinity. We don’t expect to see the oceans become fresh water.
Consider the price of gasoline. Sure it can go up and down 10-15 cents (or more these days) on a regular basis. But it is the long term trend of gases at high prices that is hurting people in the economy, i.e. the prices beign $1-$2 or more expensive than gasoline was just 10 years ago. I’ll be glad to deal with the “strong swings” of 10-25 cents if the average was only $1.50 per gallon.
Also, there is a large body of work being published trying to understand the impact of ocean acidification on phytoplankton. There is more information than I can reasonably point to but does come down to two simple points:
1) Yes, some critters will suffer due to ocean acidification, but others may thrive.
2) When you change the base of the food change (and phytoplankton are basically at the bottom), you will impact everything else in food chain.
Sure, maybe pteropods will suffer and (in an extremem case) go extinct. But now, all of the other creatures that relied on this one “insignificant” specie, will suffer, such as North Pacific salmon and cod. Now what?
The natural world modern humans adapted to has been fairly stable without major changes for the time humans have been on this planet. As big changes occur (increased levels of CO2 in the atmosphere and oceans) , which we can measure and see are much higher than they have been before humans thrived, we too will need to adapt or go extinct. I agree with folks that mentioned the Earth was been fine at higher levels. Remember, the Earth did fine with no humans for many more years than humans have existed on this planet, and can continue to do so without us.
My cod and chips crave acid and I dutifully comply
@Sensor operator says: December 28, 2011 at 1:56 pm “…The natural world modern humans adapted to has been fairly stable without major changes for the time humans have been on this planet…” The last ice age is generally considered to have hit its maximum extent around 18,000 years ago. I suggest that the shift from extreme glaciation to today’s fairly benign conditions represents a “major change.” My point is that humans adapted to the onset of the last ice age, its maximum extent and its recession. We will continue to adapt and adjust.
Dave Wendt says:
“Where exactly are they (Atlantic salmon) encountering pH values below 6.5 in the world’s oceans?”
No where. A pH below 6.5 in freshwater inhibits the osmoregulatory process of the young smolt. Once the smolt out migrate to the ocean they experience heavy mortalities as a result of the ability to adapt from fresh to salt water. Increased mortality is a result of increased bird predation as they try to ride the less saline surface waters, osmotic cataracts etc. The regrowth of the forests and the suppression of fire cycle are two of the reasons we are seeing recent lower pH in the FRESHWATER. (We are trapped into the acid rain narrative however – liming has been demonstrated to reverse this process- cheaply and effectively- but of course is attacked by environmentalists as not being natural. In fact some are now saying it is increased organic acids as the result of climate change. When scientists tried to say it was organic acids twenty five years ago AND the loss of the alkaline ash offset fire once produced – they were viciously attacked.
VIv-
Completely understand.
Alan Statham says:
“It’s a strange crusade you’re on, to try to make out that acidification cannot be a bad thing.”
What I don’t think you understand is that these “theoretical problems” steal the resources needed to address the known problems of greater relevance and threat. Oyster have declined 99% due to over harvest, reef destruction and disease. Perhaps a couple of million a year went to related research. Decades of continuing devastation- no interest. However when the opportunity presents itself for blaming fossil fuels for some theoretical threat at some future date- funding goes from a drip to a flood. Go figure?
Canada wildlife officials admitted in the 1980s that all the Atlantic salmon could have been saved for about $4.5MCdn/year by liming. Tens if not hundreds times that amount were spent on acid rain research- nothing on liming with the exception of some very recent pilot projects. So yes hyping something is bad.
I have listened to the screams that all the coral reefs were going to die- each with a different reason- each demanding huge amount of resources- and none of them ever doing anything.
Exactly what should make me consider these people care a damn about the resource.
JPeden says:
December 28, 2011 at 11:11 am
Thanks, JPeden. That’s an interesting observation, one I hadn’t heard.
w.
Well as someone with 35 years experience with aquariums, both as an armature scientist and professionally, in hard water (Phoenix) and softwater (Portland) areas, I can say that it is far easier to maintain alkali water fishes in lower PH conditions then it is to keep acid water fishes in higher PH. Some fishes used to be near impossible (well before RO, anyways) to maintain in Phoenix (tap water PH of 8.2-8.5).
The reason that one does not see marine fishes in fresh water is because of salinity. It has nothing to do with PH. The physiological changes that anadromus fishes employ as the transition between environments is an adaptive marvel.
BTW, it is interesting to note that Phoenix hobbyists have developed strains of Discus (Symphysodon discus) which normally like a PH from 4-6, able to tolerate the alkali water of the area. This shows that even in the most extreme case of an very acid loving species, adaption is possible.
John says:
December 28, 2011 at 11:24 am
Agreed.
Agreed
Agreed with caveat. The caveat is that the study covers an area that is mildly acidic because of the large sea bottom freshwater springs. This means that not only is the pH different. The alkalinity and the salinity and DIC (dissolved inorganic carbon) and the phosphorus and silicon contents are all different as well.
This means that there are a host of stressors on the corals’ ability to create a reef, and it is unclear where pH fits among all of them.
Thanks,
w.
JJ says:
December 28, 2011 at 11:52 am
You claimed that I had said that “life doesn’t mind acidity at all.” I NEVER SAID THAT. Your claim that I said that is false. Search the thread for that phrase. You will find that you are the first to say that. Not me. You.
If you don’t like something I say, quote my words. Quote what I said, exactly as I wrote it, so we can know what you disagree with. But don’t make up your own quote and ascribe it to me.
Regarding the admission of error, I am well known in the climate blogosphere specifically because I do admit my errors.
I am also an argumentative SOB who won’t allow people to falsely attribute quotes to me.
w.
Pat Moffitt says:
December 28, 2011 at 12:45 pm
Pat, thanks for a nuanced discussion of some issues regarding pH in terrestrial and freshwater conditions. Much appreciated, particularly the last statement. Deciding on the “right” pH for the ocean strikes me as being about as futile as deciding the “right” temperature for the planet.
We’re talking about a tenth and a half of a pH unit (0.15 units) being given out as the possible change by 2100. I, like you, think there are many much more important issues than this one.
w.
Sensor operator says:
‘As big changes occur (increased levels of CO2 in the atmosphere and oceans) , which we can measure and see are much higher than they have been before humans thrived, we too will need to adapt or go extinct.”
So anything higher and can be measured is how we define our major threats? If I were to make up a list of the top 100 environmental challenges we face – CO2 wouldn’t even make the list.
You mention phytoplankton- I’m much more concerned with silica deficiency and its impacts on diatoms.
For salmon- much more concerned about the loss of marine derived nutrients and large woody debris in the rearing areas and a subsidized overcapitalized fishing fleet that engages in a mixed-stock fishery.
It seems that environmental problems selected as “important” have more to do with regulatory self interest and ideological narrative than anything else.
Alan Statham,
It appears we get a completely different message from Willis’ post. I read it and thought the point of his post was to
a) show that natural variation in pH exceeds the changes predicted by climate models
and
b) use of the term acidification carries some “framing” baggage – i.e. it can give the impression that the ocean is becoming acidic.
Reading many of the comments here, I also come away with the message that just as with the climate, there is far more science does not know about what goes on in our oceans than what they know.
In the end, my conclusion is that the evidence we have for CO2 to be a “threat” to ocean life is not anywhere close to convincing in comparison to other, better defined threats.
Willis Eschenbach says:
December 28, 2011 at 4:10 pm
You claimed that I had said that “life doesn’t mind acidity at all.” I NEVER SAID THAT. Your claim that I said that is false. Search the thread for that phrase. You will find that you are the first to say that. Not me. You.
For crying out loud, you obstinant fool. Read your own damn post. You said:
“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.”
Emphasis mine, words entirely yours. And you echoed that general seniment more than once. My response to that, to which you mightily object, was:
“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.””
To which you planted your flag on the mound and claimed that (quoting you again):
“I said nothing of the sort.”
Really, Willis?
Grow up.
[JJ, the use of quotation marks means you are quoting someone’s exact words. I suggest you look into that. You claimed I had said something which I had not said. Yes, it was close to what I said, but quotation marks are not for close to, or almost, or kinda what I said.
They are reserved for things I actually said. I never said what you claimed. I objected to that, and solely that—you were putting words in my mouth I never said.
I won’t tolerate that, JJ, no matter how close the words might be to what I actually said. I pick my words with care. You don’t get to pretend I said something I didn’t say.
So read up on the usage of quotes, JJ. Because it’s obvious that, as you clearly admit above, “JJ doesn’t really know how to use quotation marks.”
What’s that? You never said that JJ doesn’t know how to use quotation marks?
My point exactly …
All the best,
w.]
Ph can be negative as well. Some acids can go to -1.
Willis, as a hard core Republican who picks up hitch-hickers and hopes one day to have you in my right hand seat, I look forward to your posts for their open, true, scientific nature…keep up the good work1
The “prologue” except in some parts that were enriched through the comments made here, is a clear scientific article.
As a matter of fact, the neutralization depends on CO2 and its resources.
crosspatch says:
December 28, 2011 at 12:47 am
“The oceans had MUCH more dissolved CO2 over the majority of the history of Earth than they do now. Earth’s atmosphere had about 3500ppm of CO2 up until only about 55 million years ago. That dropped to about 650ppm in less than 1 million years due to a single species of plant.”
3500ppm——->>650ppm
That means oceans were more neutralized in the past, and now the water seems to be less neutralized. In rivers that the water is naturally “neutral”, acidification may take place following the article views. Alkaline environment of the oceans can be neutralized by certain amount of CO2 ppm, that seems it has never happened at all and at least I have no idea about that.
With reference to the articles about the sources of CO2 “SOLAR ACTIVITIES and CO2 released by oceans/lands, it seems there can be an impact on neutralization as well as CO2 in the atmosphere. In other words, the CO2 would not remain as a permanent resident in water surfaces. It works in a cyclic system.
If we are saying man-made CO2 is less %10 of total CO2 sources, and CO2 increase in the atmosphere is more likely because of solar activities and releasing CO2 from lands and oceans, then there had been at first an increasing alkaline in water and in return, with the released CO2, the neutralization has been possible.
Here is one point; releasing/returning the CO2 would never be equal in one place and concentration of CO2 in the atmosphere would directly affect the so called neutralization.
The shadow of CO2 in the atmosphere can be seen in “neutralization” of water surfaces.
Happy new year.
Pat Moffitt says:
December 28, 2011 at 2:53 pm
Dave Wendt says:
“Where exactly are they (Atlantic salmon) encountering pH values below 6.5 in the world’s oceans?”
Sorry about that one. I was working up from the bottom of the comments and hadn’t seen your previous comments for the context of your statement. After catching up I must agree with Willis that your contributions have been both informative and valuable.
Alan Statham says: “…This is magnificently unconvincing, and you clearly don’t even appreciate that the concept of “neutral” is simply an arbitrary point on an arbitrary scale.”
It appears that your unconvincedness may be the result of your ignorance, Alan. Definition: A solution is said to be acid-base neutral if its hydrogen ion concentration is equal to its hydroxyl ion concentration.
[H+] = [OH-] There’s nothing in the least arbitrary about that. Before you weigh in here with your opinions, you might want to be better informed. Here’s a place to start:
http://www.acidbase.org/index.php?show=sb&action=explode&id=12&sid=14
Dave Wendt,
Not a problem- I took no offense from your question.
jorgekafkazar says
Definition: A solution is said to be acid-base neutral if its hydrogen ion concentration is equal to its hydroxyl ion concentration
Yes- but that is not always at a pH of 7.0 (i’m not commenting on the rest of Jorge’s statement)