The Electric Oceanic Acid Test

Guest Post by Willis Eschenbach

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

[UPDATE] I got to thinking about the “deep scattering layer”. This is a layer of marine life that during the day is at a depth of about a thousand meters. But every night, in the largest migration by mass on the planet, they rise up to about 300 meters, feed at night, and descend with the dawn back to the depths.

Looking at Figure 1, this means they are experiencing a change in pH of about 0.4 pH units in a single day … and alarmists want us to be terrified of a change of 0.002 pH units in a year. Get real.

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timetochooseagain
June 19, 2010 5:54 pm

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

R Shearer
June 19, 2010 5:58 pm

Why is the pH lower at depth?

Charles Higley
June 19, 2010 5:59 pm

Given how little we know about what is the real human contribution to atmospheric CO2, I find it incredible that the authors can begin to discuss a pH change attributable to human activity. They MUST be expressing an opinion or speculation here as they have no definitive means of determining a human influence.
As the equilibrium of bicarbonate/carbonate and carbonate and calcium ions/calcium carbonate is temperature dependent and complicated by the lower solubility of calcium carbonate in warm water versus cold, this is a more complicated system than is presented here. The two equilibrium would work against each other in response to temperature changes.
Thus, a wonderful observation of the oceans as a system about which we still have much to learn, but a meaningless discussion of human effects.

June 19, 2010 6:02 pm

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

Steve Oregon
June 19, 2010 6:09 pm

“because sea water is not acid, nor will it ever be”
ever

mike
June 19, 2010 6:10 pm

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

fred houpt
June 19, 2010 6:11 pm

Not related, but I just saw this note on the BBC.
http://news.bbc.co.uk/2/hi/science_and_environment/10342318.stm
I don’t know whether to laugh or cry. I will say that I am making an effort to read the entire and very well written ” Global Warming Advocacy Science: a Cross Examination” by Jason Scott Johnston, U of Penn, May 2010, uploaded to this site a few days ago.
As the rain blasts start to pummel my house….I bid you a warm good evening.

dearieme
June 19, 2010 6:14 pm

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

June 19, 2010 6:16 pm

Another in a string of excellent articles, Willis.
When you hot… you HOT! [apologies to the late, great Jerry Reed]

June 19, 2010 6:26 pm

And the *same* sea creatures flourish in both Hawaii and Alaska? Without any adaptation that might take a few million years? And our emissions aren’t currently accelerating?
timetochooseagain: the paper explains how they distinguished natural changes from anthropogenic changes. Natural variability is shown in the paper’s figure 3. The scale is greater than the anthropogenic variation (figure 4), but note that natural variability will add up to zero over longer time scales, anthropogenic variability will not.

Ian W
June 19, 2010 6:32 pm

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

Joe Lalonde
June 19, 2010 6:39 pm

I enjoy reading your scientific discoveries and analysis as well :~)

June 19, 2010 6:40 pm

Hey! Chemistry! My field. Awesome.
First, when CO2 dissolves in water, you get carbonic acid.
CO2 + H2O –> H2CO3
The dissolved gas concentrations are higher in colder water and higher pressures, which explains the pH closer to 7.0. This is counter-intuitive, as people think warmer solutions dissolve more stuff (which they do). But if you heat up any liquid, like a pot of water on the stove, you start seeing bubbles. That’s dissolved gas escaping as the temperature increases. So, in warmer waters, there’s less dissolved CO2, so the pH will be higher as there’s less carbonic acid.
So this “acidification of the oceans” meme is rather odd. As the global temperature increases, so does the surface ocean temperature. And when that happens, the surface can hold less CO2, which means it’s not going to be as acidic. I see the system as self regulating and something not to worry about.

etudiant
June 19, 2010 6:42 pm

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

Ed MacAulay
June 19, 2010 6:44 pm

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

Robert M
June 19, 2010 6:50 pm

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

Jimbo
June 19, 2010 6:59 pm

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


This is how I look at claims of “unprecedented” rise in [….insert climate claim…]. Whenever you look back in time we know we have had higher c02 levels than present, we know we have had higher global mean temperatures than the present and yet no runaway boiling of the planet. We are still here!
Acid Test
Are oceans becoming more acidic and is this a threat to marine life?
Biological Effects of "Ocean Acidification"
In CO2-rich Environment, Some Ocean Dwellers Increase Shell Production
Phytoplankton Calcification in a High-CO2 World
Modern-age buildup of CO2 and its effects on seawater acidity and salinity
“This paper’s results concerning average seawater salinity and acidity show that, on a global scale and over the time scales considered (hundreds of years), there would not be accentuated changes in either seawater salinity or acidity from the observed or hypothesized rises in atmospheric CO2 concentrations. ”
And finally here is a blogger’s view of the new scare or in other words funding opportunity. :o)

Ed Caryl
June 19, 2010 6:59 pm

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

eo
June 19, 2010 7:00 pm

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

Mike Davis
June 19, 2010 7:01 pm

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

latitude
June 19, 2010 7:05 pm

“‘DocattheAutopsy says:
And when that happens, the surface can hold less CO2, which means it’s not going to be as acidic””
and they claim that the slight warming right now, at our present CO2 levels, is causing the ocean to release CO2.
But at even higher CO2 levels, with even more warming, the ocean is supposed to somehow take up and hold more CO2 – making it less alkaline.
Just checked the pH in my front yard, I live on a rock in the middle of the Caribbean, it’s 8.4 Haven’t noticed any sea rise either.

Geoff Sherrington
June 19, 2010 7:07 pm

Two linked papers from New Zealand take some account of the ocean as a host for biota. I have read but not studied these, but on a quick read I cannot see any immediate objections, except to the pronunciation of “fish and chips.”
My Internet search was for terms including titration of ocean water with CO2 and pH change. There are other interesting papers. Not many deal with direct electrode pH measurement and titration with CO2, which one would have thought to be the essential starting point of any investigation of the broader topic.
http://www.seafriends.org.nz/issues/global/acid.htm
http://www.seafriends.org.nz/issues/global/acid2.htm
These papers give some answers to some questions above. Well worth a study. See especially the annual variation in the second paper under “BATS” from the Bermuda area, bottom graph for pH.

Jimbo
June 19, 2010 7:09 pm

Please Willis Eschenbach or anyone else more qualified than me take a look at the following story from the BBC. Others as well as I have read it and makes us want to cry!!!

“Ancient climate change ‘link’ to CO2”
“A “global pattern” of change in the Earth’s climate began 2.7 million years ago, say scientists. ”
http://news.bbc.co.uk/2/hi/science_and_environment/10342318.stm

latitude
June 19, 2010 7:14 pm

“”Joel says:””
Joel, rains, wind, storms, tides, upwellings, El Nino/La Nina, etc can cause very rapid, almost instant, changes in pH, salinity, temperature, Ca and carbonate levels, etc etc
Everything out there has evolved to deal with that, nothing out there is that delicate.
They ship corals all over the world in plastic fish bags, acclimate them to a holding facility, acclimate them to shipping water, acclimate them to a new warehouse, acclimate them again to a new pet shop, acclimate them again to someone’s aquarium. And all along the way their pH go up and down and all over the place.

June 19, 2010 7:24 pm

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

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

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