Ocean acidi what?

Guest essay by Steve Burnett

I have followed Wattsupwiththat for a long time, only posting occasionally if I feel an article or presentation is biased, or if there seems to be some sort of data misrepresentation. I choose to follow watts simply because there is less bias and far more numerical analysis of papers than most other climate news sources. I would certainly consider myself a climate sceptic, but my scepticism is part of everyday analysis for me, I simply don’t believe someone unless they show me the evidence.

It is evidence that is lacking for me on the warmist side of the argument; we simply don’t have a temperature record which is accurate, or long enough to infer some sort of anthropogenic effect. Proxies offer a decent long term view but are poor analogs for climatological variations in the past 200 years or so. Anyone who has worked with computer models should know, they are more likely to display what you want them to display and should always be taken with a grain of salt. Luckily I don’t have to make those arguments; there are plenty of other commentators with better credentials to make those arguments for me. I am but a lowly chemical engineering graduate, who has found neither a job nor academic position in this economy.

Within the past few weeks, a post went up which seemed more interested in ridiculing the author than refuting the claims. I was shocked, and I waited, at first it was a few days, then I let a week pass. All of those people who were more credentialed than I were silent. Certainly there was a comment on Henry’s law but nothing going into the necessary depth for refutation of the claims for doom surrounding ocean acidification. Unfortunately it’s a refutation that we need. Ocean acidification is the carbon controllers pinch hitter, the ace up their sleeve, or other analogous win card.

It’s easy to refute global warming and associated doom based on the contradictory evidence. In the case of ocean acidification its associated doom mechanism is much more difficult. To tackle ocean acidification you need to understand chemistry; pH, alkalinity, buffers, strong vs. weak acids. But you also need to grasp the math; Henry’s law, pH. and equilibrium constants. That’s why most of the time ocean acidification comes up as the last line of defense for carbon controllers, you might not understand it, but neither do they.

Before I begin I would like to acknowledge a couple of points

1. The oceans are acidifying

2. it doesn’t mean anything

If you’re not familiar with the argument here is a video produced from NOAA

http://www.youtube.com/watch?v=xuttOKcTPQs

This is an excellent reference point for us; it clearly and concisely lays out the argument. However it waves a hand over the how in favor of visual demonstrations. I will deal with these later but for now let’s talk about the processes underlying ocean acidification.

I have performed several laboratory experiments regarding CO2 and water. The first was to take a sample of river water and start mixing in atmospheric CO2. Using this method we were eventually able to overcome the buffer capacity of water and reached a pH of about 6.3. In another experiment we had a CO2 stripping column with water coming down the column and air with a variable CO2 feed going up. This experiment had already been run multiple times throughout the semester without a water changeover. Because of this my lab partner and I saw higher CO2 concentrations in our outlet stream than our inlet as the CO2 would off gas at anything below 19% concentration which was just slightly below the maximum feed we could add to our column.

To understand acidification you have to understand a little bit about mass transfer. Within a homogenous fluid, that is at equilibrium diffusion essentially forces and maintains an evenly distributed concentration. Whenever there is an interface such as an air to liquid separation then diffusion will occur across the boundary dependent on partial pressures. A partial pressure in the atmosphere can be determined by the system pressure * the percentage of atmospheric composition.

As gasses, even dissolved ones, are heated their pressure goes up, increasing the partial pressure of the material dissolved in liquid. for fixed concentrations heating will increase outgassing and cooling will increase ingassing. We know that the relationship between the amount of gas dissolved in a liquid is directly related to partial pressure so we know the relationships between liquid and gas concentrations at equilibrium will be linear with a modification to the coefficient based on temperature. This is represented by Henry’s law

p.a=k.ha*x.a Equation 1.

with the correction for the henry’s coefficient being denoted in equation 2

K.h(t)=K.h(t.0) *e^(-c*(1/t-1/t.0)) Equation 2

Of course this tells us nothing about pH, but chemistry does. pH was first conceived in 1909 by S. P. L. Sørensen. It was revised in 1924 to be used with electrochemical cells. pH represents the negative log of the hydrogen Ion concentration in solution. So at pH 7 your water has roughly 1*10^-7 moles of hydrogen ions per liter. at pH of 8 there are 1*10^-8 moles/liter of hydrogen ions. commonly the scale extends from 0-14, however pH can go into the negative range and exceed the boundary range of 14. We measure pH through electrochemical cells using the nernst equation. Seen as equation 3, R is the gas constant, T is temperature and F is the faraday constant.

E=E0-2.303*RT/F *(pH) Equation 3

pH meters aren’t simple devices. Essentially the Nernst equation measures electric potential, and plots it with respect to pH. To calibrate these instruments ideally we measure the voltage at a known pH and then at a secondary pH correcting for the slope. There are however so many things that can go wrong in a pH measurement that it is more suited to simply getting an idea of the pH rather than take a reading as gospel.

First a pH meter must be stored so as to maintain a liquid layer over the glass bulb, or else it doesn’t read pH properly. Secondly the Ionic fluid in the meter must be maintained or replaced periodically; otherwise the pH meter is likely to have a poor slope. Calibration solutions should closely match the pH of what you’re trying to measure as the linear slope is only a reasonable approximation within a few pH units. If you aren’t simultaneously measuring temperature and pH in both your buffers and the desired fluid temperature corrections can be off. In short it’s far easier to measure a 1pH unit change than a .1 and .01 and smaller increments are virtually impossible to reliably measure.

So how do we go about acidifying oceans from CO2? for that we have to consider chemical equilibrium. All CO2 dissolved in water will essentially form carbonic acid, given enough time, most of it will change back into CO2. the rate at which CO2 is converting to carbonic acid and carbonic acid back to CO2 eventually balances out so that If we know our CO2 concentration, we can know our carbonic acid concentration as well. The amount of carbonic acid in freshwater is roughly 1.7*10^-3 in pure water and 1.2*10^-3 in seawater. There is substantially less carbonic acid in seawater. So why are we concerned about ocean acidification when rivers and streams can hold more CO2? They also get direct carbonic acid from their rainfall sources. Equation 4 shows the conversion.

CO2+H2O → H2CO3–> CO2 + H2O Equation 4

Carbonic acid does not however make the water more acidic easily. Don’t forget that pH measures the concentration of hydrogen ions in solution. So of the 1.2*10^-3 moles of carbonic acid/ mole of CO2/liter only 2.5*10^-4 moles/mole/mole of hydrogen Ion are produced. This forms the bicarbonate Ion.

H2CO3- → H+ + HCO3- → H2CO3 Equation 5

Because weak acids and weak bases vary back in forth during equilibrium they make excellent buffers.

A buffer is a solution made up of one or more weak acids and bases that can be created to hold a desired pH. Essentially because the weak acids dissociate more frequently with a base present in solution and weak bases with an acid, you can hold the pH of a solution relatively stable. Your buffers pH will only change when you have consumed your entire weak acid or weak base.

The bicarbonate Ion can further dissociate but only 4.69*10^-11 of those ions do so. Now the Rub for the ocean acidification = ecosystem collapse comes from a third reaction in equation 6.

Ca(CO3)2 + 2 H+ → Ca2+ +2HCO3- Equation 6

For some it may not be baffling but let me explain the humor. Calcium carbonate is supposed to react with the Hydrogen atoms to form a free calcium Ion and 2 bicarbonate ions. But wait, the equilibrium concentrations are still going to hold. So as CO2 increases, carbonate Ions the ions “under attack” by ocean acidification WILL ALWAYS INCREASE IN CONCENTRATION!!!!.

But how does that relate to biological organisms. In short anything that needs to make use of carbonate will benefit from an increase in its supply. But there is actual math here too. Behold the Monod equation for microorganism kinetics. U is the specific growth rate, umax is the maximum growth rate, s is the concentration of the limiting substrate and ks is the value of u where u/umax is .5.

u=umax*(s/(k+s)) Equation 7

Essentially what this states is the growth of an organism is tied to the limiting nutrient. So we can conclude that as CO2 increases, Carbonate ions increase, which means that the limiting nutrient for shell production cannot be carbonate. If it was, then an increase in CO2 would correlate to a similar increase in growth for the carbonate dependent species. In the event that carbonate was in such comparative excess there is no conceivable means for the species to be struggling as all of the aqueous carbonate would be consumed at a substantially higher rate than CaCO3 precipitate.

All of this is ignoring the buffer capacity of the oceans; it is immense and tied strongly to the carbonate system. While you can increase the amount of carbonic acid in the sea, in order for CO2 to induce a pH change you would need a massive amount of it both dissolved in the ocean and with a high concentration above in the atmosphere. It is essentially chemically impossible for ocean acidification from CO2 to induce harm on carbonate dependent species. Before we can ever truly figure out whether or not CO2 is causing a problem we need to know the rate the shells are dissolving compared to the rate they are being formed.

Great, now we understand some of the physical, chemical and biological processes underlying the ocean acidification=doom argument. In order to determine the actual effect of increasing CO2 concentration in the atmosphere we have to look at the concentration of CO2 and temperature at 2 points in time as both are changing. For my example I decided to use the EPA’s stated 1.5C temperature increase since 1917 and an increase from 280ppm for my concentration. I used 10C as my current water temperature and 390ppm as my current CO2 concentration. Atmospheric pressure was assumed at 1atm. I also kept hearing a pre-industrial pH value of 8.2. This calculation is done under the assumption that preindustrial pH system was stable and thus increases from emissions will essentially add to the previously existing H+ concentration in the solution.

Our partial pressures for CO2 therefore turn out to be

PreI=397.14 Pa

Modern=553.234 Pa

The modified henry’s coefficient

KhPreI=18.205L*atm/mol

Khmodern=19.191LAtm/mol

Which means our concentrations for preindustrial and modern CO2 are given by equation 8.

C=P/Kh

And the values

PreI=2.153*10^-4 L/mol

Modern=2.845*10^-4 L/mol

Which gives us our H2CO3 concentration in both scenarios

PreI= 2.584*10^-7

Modern=1.476*10^-7

I only used the first dissociation constant as the concentration was already in the 10^-11 values so a 10^-22 values wouldn’t have been significant Leading to a total H ion concentration (from CO2) of

PreI= 6.46*10^-11

Modern=3.69*10^-11

OF course the net difference between these two values

Modern-Prei=2.075*10^-11 H+ ions in solution

So the change in pH is equal to -log(H+new+1*10^-8.2)

so roughly the total increase in carbon emissions has changed the pH to roughly 8.199

That’s not even measurable. In order to see the claimed pH increase the atmospheric increase in CO2 would have to be 100x greater than what has occurred. Surely we can say the acidity, a measure of h+ ions has increased 30% but that’s guaranteed from the chemistry and tells us nothing about the oceanic quality of life.

See to do that we would need to perform an experiment and actually collect data. Unlike global climate change these studies are comparably simple. Get a bucket and a CO2 tank add some corals and oysters and other carbonate loving critters and then set the atmospheric CO2 concentration above the water, find out what happens. Repeat the study for pre-industrial, modern double modern and prehistoric levels of CO2 simply add food and allow Ion exchange. In less than 5-10 years someone could conclusively prove CO2 is causing harm.

Even if you didn’t want to actually collect data there is one other scientific principle that the carbon controllers are violating. That’s the correspondence principal; we can look back at history and watch how CO2 trends match with carbonate critter fossil records. If we actually look back far enough to when CO2 was at its peak levels on this planet we find that most of our mollusks and carbonate dependent organisms evolved at the same time our atmospheric CO2 concentration was over 8,000ppm. Before anyone gets to claim that carbonate organisms are having problems they need to answer why they can’t deal with a CO2 increase of 30% while their ancestors thrived at concentrations higher than 200%. It just doesn’t make sense.

But what about that video?

She starts with 2 clear and noncontroversial statements and then 1 that is somewhat controversial, at least for me. Specifically that increased acidity makes it difficult for Calcium carbonate Ca(Co3-) dependent organisms to survive.

For her first demonstration she drops a block of dry ice into water and and we get to see some bromothymol blue change colors from blue to yellow. So yes she demonstrated that CO2 does make water more acidic. But she also clearly mentioned Atmospheric CO2 having an impact on ocean acidity. By dropping pure CO2 into the water it is essentially creating a system with 100% partial pressure at the liquid vapor interface. Essentially they are increasing the atmospheric CO2 by a factor of 3000.

The second demonstration was more of the same shenanigans. First they divvied up acetic acid vinegar, not carbonic into three concentrations; 1 with none, one with half and one with a concentration straight from the bottle. She then added some calcium carbonate, OOO fizzies. so yes the acid does react with the shell and outgasses CO2. No kidding, that has what to do with a carbonic acid/carbonate system? and that glazes over the fact that a CO2/carbonic acid system has a pKa value of about 6.3, acetic acid is closer to 4.8 it has both a substantially higher dissociation constant and does not form a carbonate complex. Essentially the demonstration showed nothing.

But then came the classic heartwarming moment. The swimming little critter in the oceans of tomorrow, heart wrenching I know. Except wait they took a thin walled shell with no critter and placed it in a solution of unknown composition, with a pH value expected in the oceans of the future, slowly the shell dissolved, really slowly, over several days the critters shell became transparent, oh how sad. For that whole time lapse they could have used two identical shells; one in modern seawater and the other in a tank with a controlled CO2 atmosphere. Instead they literally ch

ose the most meaningless way of demonstrating nothing, they didn’t use a chemically similar environment and they didn’t use actual organisms who regenerate their shell and that is fascinating.

So if you have made it this far and your head hasn’t exploded congratulations Here are some bullet points.

1. It is Interesting to note that we somehow have an accurate measurement of ocean acidity from 200 years ago when the apparatus to measure pH was only invented in 1924 and it wasn’t conceived as a measurement until 1909. It should be impossible to conclude within .1 pH unit the actual oceanic pH 200 years ago.

2. The maximum possible change from atmospheric CO2 pre industrial to today is less than .001 pH units, it is thus impossible to measure

3. Even if we could measure .001 pH units there are plenty of questions on the accuracy and calibration techniques associated with the measurement

3. It is impossible for CO2 to deplete carbonate ions in solution

4. Rivers and freshwater lakes are more susceptible to carbonic acid from atmospheric CO2, so why are we worried about the oceans?

5. It is essentially chemically and biologically impossible for carbonate dependent organisms to suffer from CO2 increases

6. Carbonic acid is not the same as hydrochloric or acetic acid.

7. pH from carbonic acid tells us nothing about the CO2/Carbonate system

8. There have been no experiments to demonstrate harm, only hypothesis and models.

9. The experimental framework for testing carbonate organisms with increasing CO2 is easy, yet unperformed

10. The organisms most susceptible to ocean acidification from CO2 evolved at a time when concentrations were 15 times higher than today.

11. Ocean acidification means nothing if the rate at which CaCO3 is being produced exceeds the rate at which carbonic acid consumes it.

12. The buffer capacity of the ocean is huge and incorporates carbonic acid, further demonstration of CO2 overwhelming this buffer is needed.

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GlynnMhor

In addition, even if it were possible to demonstrate some deleterious change due to changing pH, most of the shelled organisms have a reproductive strategy that involves thousands or even millions of larvae, of which a few percent at most will survive to adulthood.
And whatever the preferred pH of today’s adults, the few larvae that survive will tend to be the ones better suited to the new pH. So even if the individual organisms cannot adapt quickly, the overall population can.

jorgekafkazar

“…Anyone who has worked with computer models should know, they are more likely to display what you want them to display and should always be taken with a grain of salt.”
I recommend the 100# bag, in the case of climatologists’. And clamatologists’, as well.

noaaprogrammer

What would happen if, as some carbon sequestration proponents propose, the oceans were strewn with iron to increase the bloom of micro organisms, which upon death sequester the carbon as calcium carbonate on the ocean floors?

Ryan

“10. The organisms most susceptible to ocean acidification from CO2 evolved at a time when concentrations were 15 times higher than today.”
No they didn’t lol. Their ancestors did. The species alive today have not contended with 500+ ppm CO2 in a LONG time. And they experienced massive die-offs at all classification levels during rapidly-shifting atmospheric gas levels. Geologically rapid that is, which is usually slow compared to the speed we are releasing CO2.
I guess it’s just refreshing to see someone who isn’t trying to blame rising CO2 on nature.

davesivyer

well presented, Steve!
It is pleasing to see someone use their broad and applicable knowledge in such a clear, meaningful way. Good luck with the job hunt.

Mike Ford

Whew, my head didn’t explode. Excellent article and good luck job hunting.

Some experiments with living creatures have been carried out, corals suffered slightly with increased CO2, but crustaceans such as crabs lobsters and shrimps actually increased shell thickness and density

”1. The oceans are acidifying”
I almost stopped reading after this misleading statement.
Sorry, but oceans are not acidifying.
“They are becoming less alkaline.” would be far more accurate.”|(slightly in there might look good too.)
However, I dallied, continued and read the whole article. Congratulations for this great info.

Goldie

Nicely done – Also its probably worth bearing in mind the quantum of mineral calcium carbonate present in rocks and sediments in the sea or on the coast that would fall “victim” to acidification long before the calcium carbonate being laid down by living organisms.
I really think that this is a case of a little knowledge is a dangerous thing.

OldWeirdHarold

“4. Rivers and freshwater lakes are more susceptible to carbonic acid from atmospheric CO2, so why are we worried about the oceans?”
——-
That’s a really good question.

Thanks, Steve. Very good article.
Less alkaline is a better description for this.

Dr Burns

A couple of references I’ve checked, such as this http://www.fao.org/docrep/003/y1899e/y1899e09.htm suggest that your equation 6 is driven to the right, not left, as CO2 increases.

dalyplanet

Excellent post. You have very well clarified this interesting and technical aspect of the climate debate.

stan stendera

Kudos. Bravo. Thank you Steve. As for the job hunt, a lot 0f scientific and industry heavy hitters read this blog. After this tour de force I’ll bet you have valid job offers tomorrow and take a job in a week or less. Come back and post at least a comment on how it goes. I, if I could, would try my best to hire you tomorrow. Again Bravo!! Maybe our education system is producing at least a few creative thinkers.

stan stendera

Thank you Anthony for finding and posting this article. The work you do for science will someday be recognized.

True, true, the oceans are infinitely buffered.

Don’t know where you live Steve, or what your interests/speciality is, but there are lots of chemical engineering jobs available in Alberta.

James Allison

Head almost exploded but I held on – Great article thanks Steve!

markx

Excellent iArticle and information… On a hugely buffered system…
No mention of carbonate compensation depth?
Below a certain depth (temperature and pressure related) shells will dissolve… recent published scare papers dwell on the fact that this depth will change (By how much? Millimetres? Metres? ) in a higher dissolved CO2 environment… and upwellings of that water are “expected to be” more common…
So this is just business as usual for these organisms…

wakeupmaggy

You helped us who don’t really speak physics and math get the big picture. Thanks, I read the whole thing. I’m sure nature will sort it out, as we are nature too..

Thanks, Steve, for a long-awaited, chemical analysis of how we have been conned to believe the OA-thing. I have done some deep-analysis of how the shenanigans have been going about to underpin their beliefs. Here is one of the articles:
In a newly published report by Jantzen et al. (2013) on the occurrence of cold water corals and some strange natural pH-gradients in the Comau fjord of Chile, the fact about groundwater springs in the fjord are not taken very seriously: “CO2 and H2 S may degas and further promote the formation of CO2 -rich and low-pH water ‘bodies’, which ascend to lower depths. Further hints for such a scenario are given by observations of white mats of chemotrophic sulphur bacteria of the Thiooloca- and Beggiatoa-group and ‘foul eggs smell’ at sites where low density water seeps out of cracks (Gallardo et al., 2005). These bacteria are usually associated with low oxygen environments.” But even so, the authors find excuses for not taking account of the positive effects of the seeps on the corals: “Nevertheless, the relatively high oxygen situation in deeper water may be indicative of little or no hydrogen sulphide release, low oxygen consumption and sufficient water exchange with oceanic water masses.” And further: “Variations of pH may therefore be determined by CO2 -rich water production, rather than by a daily cycle (i.e. by photosynthetic production, respiration or tide). Nevertheless, daily fluctuations in pH can reach ~0.2 units within day-and-night cycle.” It seems the possibility of nutrients (minearals) from the seeps feeding into the fjord ecosystem is ignored by Jantzen et al. (2013). But even so, the fact remains that the deep-water corals live in water previously thought to be poisonous to them: “This suggests a high adaptation potential of D. dianthus to adjust its calcification performance to conditions thermodynamically unfavourable for the precipitation of aragonite.” (Jantzen et al., 2013).
Jantzen C., Häussermann V., Försterra G., Laudien J., Ardelan M., Maier S. & Richter C., in press. Occurrence of a cold-water coral along natural pH gradients (Patagonia, Chile). Marine Biology. (subscription required).
See more about the Comau fjord here: (www.oceanacidification.wordpress.com/2013/05/22/occurrence-of-a-cold-water-coral-along-natural-ph-gradients-patagonia-chile/). (Although this is a very interesting summary of their research, Dr Claudio Richer manages to ‘hide’ a very obvious and important fact about the Comau fjord: The fjord contains cool (volcanic) springs along the shores and undoubtedly along its underwater axis. There is little doubt that these hydrothermal springs (seeps) have the same effect on the seawater pH-value as the seeps in the Red Sea, i.e., a bulk lowering of the pH-value. The fish farmers in the fjord from where the ROV was borrowed by the AWI-researchers, know this and also the tourist operators in Chile (see for example: http://www.exchile.com/downloads/Coast_of_fjords_SeaKayak.pdf).

Um, any consideration for the mega tons of manganese nodules on the ocean floor? That’s a huge load of metals that will resist any “acidification” (not to mention all the carbonates and other deposits…) I think the buffer capacity is grossly under rated.
BTW, there is an existence proof of shellfish doing fine in really acid water. Fresh water species:
https://chiefio.wordpress.com/2012/03/08/clams-do-fine-in-acid-water/
Back on those metals… What happens when a metal carbonate salt is added to an acid pool? It becomes more alkaline…
https://chiefio.wordpress.com/2011/08/01/lessons-of-the-pool/

pH and CO2
My first week, I was busy adjusting the chlorine and getting the total alkalinity right along with a couple of other minor things. The pH was reading ‘quite low’ at 6.2, but we didn’t have any “pH Up” chemicals. Finally, the day came to address the pH (as I’d got the rest where I wanted it). Finally I remembered that the ‘low reading’ on a test strip had no real “lower bound”, it just meant “this far OR MORE”… So I hit the pool store for an alkalinizing chemical.
What do they sell to make a pool more ALKALINE? To RAISE the pH from acid to basic?
Sodium Hydrogen Carbonate or Sodium Carbonate. Baking Soda and “Washing Soda”. This stuff is sodium with a carbonic acid group (i.e. CO2 hydrated) or two stuck on it.
To make the pool more alkaline, you dump in loads of CO2.
I put in about 8 pounds of Sodium Hydrogen Carbonate, and moved the pH to an indicated 7.3 or so on the dipper.
Clearly all that added carbon dioxide was unable to make the water acid… (In fact, it leaves the acid water, letting the sodium stay behind, to make it alkaline. So if an acidified river runs into the ocean, carrying it’s load of dissolved salts and CO2, the CO2 will leave the ocean to make it more alkaline. That is the Lesson Of The Pool for pH.

So it is not just a pedantic point to say that added CO2 is making the ocean less alkaline. Once the ocean actually does try to become acid, the CO2 will out gas heavily and prevent it.
It also is not pedantic to point out the ocean bottom is strewn with megatons of metal in the form of nodules. They, too, will prevent acidification. We have excess of metal and metal ions in the ocean, and the CO2 can leave if it isn’t alkaline.
There is a reason the ocean is alkaline. That same reason will keep it alkaline…

I was enjoying the read until Equation 1. Some definitions, please!
I assume that t is temperature.
But what are:
p.a, k.ha, x.a, K.h(), c, t.o, E, EO …
(and at that point I stopped reading).

gregole

Steve,
Nice.
Here’s my take home:
H2CO3- → H+ + HCO3- → H2CO3 Equation 5
Because weak acids and weak bases vary back in forth during equilibrium they make excellent buffers. A buffer is a solution made up of one or more weak acids and bases that can be created to hold a desired pH. Essentially because the weak acids dissociate more frequently with a base present in solution and weak bases with an acid, you can hold the pH of a solution relatively stable. Your buffers pH will only change when you have consumed your entire weak acid or weak base.

And:
1. It is Interesting to note that we somehow have an accurate measurement of ocean acidity from 200 years ago when the apparatus to measure pH was only invented in 1924 and it wasn’t conceived as a measurement until 1909. It should be impossible to conclude within .1 pH unit the actual oceanic pH 200 years ago.
2. The maximum possible change from atmospheric CO2 pre industrial to today is less than .001 pH units, it is thus impossible to measure
3. Even if we could measure .001 pH units there are plenty of questions on the accuracy and calibration techniques associated with the measurement
3. It is impossible for CO2 to deplete carbonate ions in solution

All the kooky claims that Man-Made CO2 is destroying (fill in the blank) seem time and again to depend upon misstatement or misapplication of physical law combined with poor measurements or claims of better measurements than possible with little or no uncertainty analysis coupled with a complete disdain for empirical evidence.
Thanks for taking your time to post.

Streetcred

Nice article, Steve. I propagate sps corals … acropora sp., etc. Recently I had a marine biologist (nice bloke) from the university department of a particular rabid warmista come and have a look at my systems. In passing, he admitted to me that, despite their level of technical capability, they were unable to successfully grow acropora’ let alone sustain it in a comatose state. This tells me that they would not be able to sustain an organism in sufficiently good health to be able to conclude any specific outcomes for ocean acidification studies utilizing live organisms.

Gail Combs

“….See to do that we would need to perform an experiment and actually collect data. Unlike global climate change these studies are comparably simple. Get a bucket and a CO2 tank add some corals and oysters and other carbonate loving critters and then set the atmospheric CO2 concentration above the water, find out what happens…..”
You are missing an important part of the environment – ROCKS. (or more properly the lithosphere.) Minerals dissolve and form part of the buffer system. This is the part the scare merchants leave out.

….Furthermore, this carbonate buffer is not the only buffer active in the atmosphere / hydrosphere / lithosphere system. The Earth has a set of other buffering mineral reactions. The geochemical equilibrium system anorthite CaAl2Si2O8 – kaolinite Al2Si2O5(OH)4 has by the pH of ocean water a buffer capacity which is thousand times larger than a 0.001 M carbonate solution (Stumm & Morgan, 1970). In addition we have clay mineral buffers, and a calcium silicate + CO2 ø calcium carbonate + SiO2 buffer (MacIntyre, 1970; Krauskopf, 1979). These buffers all act as a “security net” under the most important buffer: CO2 (g) ø HCO3- (aq) ø CaCO3 (s). All together these buffers give in principle an infinite buffer capacity (Stumm & Morgan, 1970)….
http://www.co2web.info/ESEFVO1.pdf

DesertYote

I have actually ran a Reef Aquarium (300L) with CO2 injection just to see what would happen. My corals did just fine. The coralline algae was glorious and the green algaes thrived. All in all, it was a stable and very happy Aquarium.
I just got back from Santa Rosa where I clear out my storage. It has been broken into several times; lost a lot of stuff. I was not able to find the most important of my notebooks, and it was 20 years ago that I did this experiment so I don’t remember the details that well, but I had to really crank up the bubble rate to have any measurable impact on dissolved CO2. My impression is that far more CO2 goes into the atmosphere from the ocean, then the other way around. Far more CO2 is produced by eukaryote metabolism then from all other sources combined.
BTW, my fresh water experiments were far more interesting. I was investigating the role of fungus. Never underestimate the power of fungus!

rgbatduke

One additional point. The pH of the ocean is not constant as it is. From the equations above, it couldn’t be! Even if it is in equilibrium with a well-mixed gas on top, sea surface temperatures vary wildly from summer to winter, from tropics to the poles, from the surface to the depths. Indeed, the pH isn’t “8.2”, it is anywhere in a general range from 8.2 to 8.5.
The specific claim made detailed e.g. here:
http://www.ocean-acidification.net/FAQacidity.html
is that while there is a surface layer of the ocean that is saturated with calcium carbonate so that it does not tend to dissolve, if one goes down far enough one reaches a level where the water is undersaturated and shell material will tend to dissolve. Decreasing ocean pH — which they do predict will occur on a remarkably aggressive time scale — supposedly decreases the depth of the saturated layer, presumably squeezing the ecosystems of shell-building marine organisms. They also claim that pH has already dropped by 0.1 from the beginning of the industrial revolution, and will drop by another 0.2-0.3 by 2100 if CO_2 doubles etc.
Now, I’m not defending their assertions, but playing the devil’s advocate here you are asking me to believe several things. One is that the authors of all of the papers listed on ocean acidification are ignorant of the basic chemistry of the ocean, or that they are making an assumption that is radically different from the assumptions you make above. Another is that there is no interesting dependence on the KIND of calcium carbonate in marine shells — you seem to be lumping aragonite and calcite into a single barrel where marine organisms tend to form shell materials out of one or the other if I understand things correctly. Aragonite seems to be tied into reef ecology and in fact is the buffering material that keeps pH comparatively stable.
It doesn’t seem to me that you have provided a sufficient argument to demonstrate either that the pH of the oceans will not change by 0.1 to 0.3 with increased CO_2, when there is already a variation in pH of almost this amount naturally due to many factors including variations in local chemical equilibrium in warmer and cooler waters throughout the ocean body itself, or that you have adequately addressed the impossibility of the upward movement of the boundary layer between definitely undersaturated deeper/colder water and saturated upper/warmer water. Surely if this boundary does move up across a deeper zone inhabited by species specific to that zone (a coral reef, an underwater shelf) it might cause problems for the species living there. You really should read and address specific issues with the assertions in the actual literature — not being familiar enough with the latter myself I cannot tell if you have erected an enormous straw man, or straw reef, by asserting correct things that they would even agree with that have nothing to do with whether or not there could indeed be a problem.
With that said, I agree that there are certain parts of the argument on even this FAQ that I find un-credible. For example, one of its references is entitled “The Future Oceans: Warming Up, Rising High, Turning Sour”. The current evidence is that yes, they have warmed by as much as a degree or two post LIA, and they are not unlikely to warm up another degree by 2100. They have risen up by 9 whole inches since 1870, and they might rise up another whole 9 inches — or what the heck, let’s say a whole foot — by 2100. These things are therefore technically true, although no one complained about either one until they were told that this was the harbinger of a future “catastrophe”.
However, there is no way in hell dropping oceanic pH from 8.1 (say) to 7.9 is turning the ocean “sour”. Nor is this going to affect any sort of shallow-water mollusks — the saturated/unsaturated boundary is far from the surface in almost all of the world’s oceans, with the exception being the cold polar regions because they are, well, cold. Here they shoot themselves in the foot, as warming confounds movement of the boundary. If the polar oceans are warmer, then they will naturally increase the thickness of the saturated layer and one has to do a complicated analysis to see what the net effect is on the unsaturated/saturated boundary. Their “worst case” expectations appear to be a very solidly basic ocean, not sour at all, considerably more basic than fresh water.
One further complaint I might have with this FAQ is that it rather obviously suffers from the usual short/long timescale mixing that climate science uses to build meaningless hockey sticks. In its very first graph, it displays Oceanic pH over the last 25 million years. As usual, there are no error bars or explanations as to how they might know, but they show a smooth variation from roughly 8 to a peak of almost 8.4, a series of sawtooths generally down with the entire Pliestocene being more or less the final jig downwards. But then at the very end they show 1800 as a sudden jig up! 2000 as an equally dramatic jig down! An unexplained dot that is the terminus of the smooth curve! Two more terrifying dots way down at 2050 and 2100!
But they were dead on the dot at 1800. All they’ve showed is that their million year timescale graph is crap, because it smooths/averages over VERY long periods — tens of thousands of years or more. We have no idea if the pH bounced up and down by 0.1 or even 0.3 on timescales of decades or centuries all throughout this time. In fact, one can hardly imagine that oceanic pH didn’t bounce right along with the various major glaciations in the late Pliestocene, e.g. the Wisconsin glaciation. Whether or not their projections for 2050 and 2100 are right or wrong, their graph does nothing whatsoever to indicate whether or not such variation is unusual, unknown, or even occurring at an unusual “rate” (since the text clearly states that the values themselves are not alarming, it is how rapidly the change is occurring that has them worried, supposedly too fast for the species to evolve to accommodate the change?).
But we do not really know the average pH of the oceans during e.g. the LIA, let alone the specific pH of individual coral reef environments or the arctic. That is one thing in your article I completely agree with. They make a statement — that oceanic pH has dropped by 0.1 from 1800 — that I would be very, very interested in seeing justified, with the missing error bars. I would wager that the error bars are larger than 0.1, meaning that we have no idea what the oceanic pH has done since 1800. Perhaps we know from 1950 to the present. Perhaps.
In any event, your article is interesting, but a bit incomplete and not any more convincing than the FAQ itself in the end. I find that I can still believe that comparatively small shifts in oceanic pH could be “disastrous” for at least some marine species living in waters that for one reason or another are already marginal habitat, if they do indeed happen too fast for the stressed species to evolve. I don’t think you’ve adequately demonstrated that those changes cannot and will not occur with increasing CO_2. Neither do I find the FAQ with its misleading and error-bar free graph stated as a matter of certain fact and its assertions of carefully unspecified eco-disaster to be convincing, and I find its obviously political overstatement of the science to be a bit offensive. (Turning sour? Ha!)
Which leaves me where I began. I don’t know if there is something to the threat or not. I doubt that anybody does, really. We’ll probably only find out when oceanic species start to drop dead in droves from a “rapidly changing” pH — or don’t. And we will find out, because barring the invention of cold fusion or the wholesale investment of the resources of the United States in e.g. LFTR and a couple of breakthrough discoveries in solar technology and batteries, the industrializing third world countries are going to burn carbon whether we like it or not until their life style is just as good as ours is, as long as it is the cheapest energy out there and really the only game in town economically feasible to play.
This will either carry the world oceans solidly over towards the 2050 values or not. Indeed, given that almost a decade has elapsed since many of the papers even in this FAQ were published, given the “dramatic” change they predict/claim, we should be roughly 1/12 of the way there. By 2020 there should be little doubt whether they are right or wrong. In the meantime, nobody is going to change their carbon-consuming behavior at the expense of civilization, either holding onto what they have or reaching for what they have not.
rgb

Nicely done, Steve. I wasn’t sure where this article was going and somewhere about the first minute of the NASA video I was sputtering and throwing things. Somewhere in my misspent youth I picked up 3 degrees in chemistry, postdoctoral research and a couple of decades in the chemical industry. Most of that time If I had been at a presentation like the NASA video, the presenter would have been laughed out of the place. Actually one that bad and the presenter would have been hooted off the stage. The NASA video was intellectually dishonest to a point that I found truly offensive. Some of the terminology was technically correct, but, as Steve very aptly pointed out, her demonstration was intentionally misleading and pure hokum. Ocean acidification is a scary term if you believe we are turning the oceans into something that would cause sea shells to fizz. And she lead you to believe that with her little demonstration. Absolutely disgusting.
The warmists can’t win in the arena of ideas, so they resort to stuff like this. And this is supported by our tax money.
One of my lesser talents is patching drywall. I’ll get to hone those skills because of flying objects from the video.

Anthony H.

Since CO2 comes out of solution at warmer temperatures, shouldn’t the oceans get more alkaline as a result of warmer temperatures? Proponents of CAGW says that increased atmospheric CO2 will made the oceans acidic (less alkaline) but as you point out, this makes little sense. Shouldn’t they get less alkaline in cooler temps, as CO2 is forced back into solution? Or am I totally confused?

HankH

Steve, thank you for an excellent post. It has been bookmarked as one of my references.

DesertYote

rgbatduke says:
July 8, 2013 at 9:49 pm
One additional point. The pH of the ocean is not constant as it is. From the equations above, it couldn’t be! Even if it is in equilibrium with a well-mixed gas on top, sea surface temperatures vary wildly from summer to winter, from tropics to the poles, from the surface to the depths. Indeed, the pH isn’t “8.2″, it is anywhere in a general range from 8.2 to 8.5
###
I would never claim to know the pH of a small Aquarium with accuracy of less the +/- 0.5 pH let alone an ocean, even with my trusty Hatch, and I am a trained and very experienced professional in making such measurements. Test and Measurement is my livelihood.

Peter Foster

Excellent article but surely you forgot something. Limestone forms at a rate of about 40mm/1000 years
This equates to the deposition of 4 million cubic metres per square km/100,000 years multiplied by 200 million km^2, roughly the area of ocean less than 4500m deep (carbonate compensation depth, CO2 dissolves below this level) = 800 x 10^12 cubic metres/100,000 years. Now multiply by the average density of limestone -say 2.4 tonnes/cubic metre gives 1920 of calcium carbonate. of which 44% was derived from CO2 =845 x10^12 tonnes.
So changing this from 100,000 years to one year gives an annual precipitation of 8.45 gigatonnes of CO2 removed from the oceans each year.
In addition the increase in photosynthesis and plant growth as a result of increased CO2 would remove a few more gigatonnes of CO2 but I do not have the data to calculate that.
After all that happens is their any increase in oceanic CO2/HCO3/CO3 at all ?

GregK

Regardless of small scale laboratory experiments, though not doubting their usefulness in exploring specific details of processes, my training and experience as a field geologist leads me to the belief that field evidence trumps the lab.
So to the ocean acidification story and its effect on calcareous life.
Fringing the Kimberley in northern Western Australia is a fossil carbonate reef system that was almost as big as the present Great Barrier Reef along the Queensland coast.
[see http://www.pesa.com.au/publications/pesa_news/oct_nov_09/images/pn102_75-77.pdf ]
It formed during the Devonian, from around 419Ma to 358Ma [don’t give up yet dear reader].
Atmospheric CO2 levels at the start of the Devonian were 10 to 12 times higher than current levels [around 4000 to 5000ppm] but the sea was not a carbonic soup. Critters survived and prospered. On the evidence of fossil remains I would suggest that concerns regarding ocean acidification are overstated to say the least.
Interestingly by the end of the Devonian CO2 levels plunged to around present day levels, accompanied by glaciation and mass extinction.

Kasuha

jimshu says:
July 8, 2013 at 8:44 pm
”1. The oceans are acidifying”
Sorry, but oceans are not acidifying.
“They are becoming less alkaline.” would be far more accurate.
____________________________________________
When you’re standing near the South pole and go away from it, you may insist that you’re becoming less southward but you are still going North. It’s just a wordplay with no practical meaning because your motion doesn’t depend on how you call it.
I’m happy the article did not fall for this wordplay and provided concise analysis instead.

higley7

1. You have to use the complex buffer that we call sea water. River water is not sea water.
2. The oceans are NOT acidifying. They are still on the basic side and entirely within the normal range of fluctuation.
3. Photosynthesis is a very basic or alkalizing process and, in bays and estuaries, can raise the pH to 10–11 on sunny days. Organisms are quite able to handle this radical change.
4. If nothing unusual is happening, then what is the problem?
5. Most of the studies looking at ocean acidification acidify the water and look at how certain organisms react. Ocean acidification, if it did occur, would be slow enough for organisms to adapt easily.
6. As CO2 has been very much higher than now for most of the last 600 million years, why on Earth would people think that they could not handle a small change now?
7. The pH of the sea water is not what is important. It’s the pH inside the organism that counts and biological processes have no problem handling any changes that might occur with much higher CO2. The proof is that these organisms are here now. The Cliffs of Dover were not built during low CO2 conditions, but when CO2 was as much as 5–10 times higher than now—the organisms loved those conditions.
8. Around the world coral reefs are thriving as CO2 is food and they could not care less that there is a slight change, if at all, in the pH.

AlecM

Earlier on noaaprogrammer stated that phytoplankton sinks to form carbonate. It doesn’.
The biomass forms polysaccharides the greatest store of carbon. There is slow equilibrium with CO2 and carbonate/bicarbonate.

higley7

9. Any protons released by the formation of carbonic acid in water cannot affect the equilibrium leading to calcium carbonate. A product of an equilibrium cannot affect itself. Only an outside source of protons could alter the equilibrium, such as a huge influx of sulfuric acid from a volcanic eruption. Fortunately, sea water is a complex buffer and it is rather difficult to alter the pH.
More CO2 means MORE calcium carbonate and more coral reefs not dissolving reefs. THey have that chemistry backwards.

Janice Moore

Mr. Burnett! WELL DONE. Your article is in my WUWT Top 5 (so far). You did much for the sake of truth, today. Perhaps, that is why your job (it IS coming) was delayed. That article took a lot of time, I’m sure! Yes, indeed, Steve Burnett stood up and we all saw what a Science Giant he truly is.
***********************************************************************
POSITION WANTED (for Burnett): Exceptionally bright, highly motivated chemical engineer; superb writing ability; fine attention to detail. References available from WUWT scientists.
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“Proponents of CAGW says that increased atmospheric CO2 will made the oceans acidic (less alkaline) but as you point out, this makes little sense.” [Anthony H. at 9:58PM, 7/8/13]
Correct. Your confusion arises from your temporarily having forgotten what the CAGW folks are all about: CONTROL. In order to control the energy market, human CO2 must cause global WARMING. It clearly isn’t doing that. Their hocus pocus [“makes little sense”] solution? THE CO2 IS HIDING IN THE OCEANS (we know this because …. the MODELS and our big fat lies say so). Like “The Blob,” dumped into the Arctic Ocean in 1959, human CO2 is lurking in the briny deep, juuuuust waiting to………………….. COME AND GET US. So, buyourwindmillsandsolarpanelsandcrappylightbulbs NOW to….. uh………. to avert certain disaster.
LAUGH-OUT-LOUD — who do they think they are fooling? NO ONE! Either people are too busy or uninterested in their propaganda to pay attention to it (these people are not fooled, they are just not engaging), or they see the truth.
It is only a matter of time until the pack of AGW cards lies strewn over the lawn, helpless, to be blown away by the winds of time, one…. by one………… by one.

DonV

Steve, thanks for taking the time to think through and then pull all of the known “facts” together so that we could follow both your logic and your application of the known classical chem. eng. equations to their logical conclusions. Reading your excellent post, I felt like I was back at school having the TA explain the how to solve the fifth problem on the ChE Thermodynamics final!
Reading the original post that prompted your response, my initial reaction was, this person
I had a couple thoughts that I’d like to interject that came to me while reading your post.
First, I have often read that climate scientologists consider CO2 in the atmosphere to be uniform, well mixed, and having a slow turn-over rate, which is the reason why they rely on the CO2 concentration as measured on an active volcano in Hawaii as the “world’s standard” reference concentration. It seems to me however, that the water vapor that is transported up to and then condenses in low clouds and freezes in high clouds only comes into equilibrium with gaseous CO2 AFTER condensation has occurred. Please correct me if I am wrong, but doesn’t this mean that clouds and rain act as a scrubber to remove CO2 from the atmosphere. I would think it would be a simple experiment to measure the CO2 concentration of the air during a rainstorm to show whether the assumptions about CO2 being “uniform, well mixed and having slow turn-over”. If tiny little (ie. high surface area) droplets of water are used to scrub SO2 from flue gases, and the first CO2 scrubber used in a submarine used water as the primary solvent, it would seem to me that storms are nature’s “scrubber” and actively serve to maintain a balance between atmospheric CO2, and the CO2 dissolved in all of the water in the world – the vast majority of which is very strongly (even actively) buffered ocean.
So then the second thought follows on the first. The follow up to your post should be to determine the change to the mass balance. If rain effectively scrubs CO2, yet the concentration of CO2 on Mauna Loa continues to increase, either:
1) The CO2 concentrations as measured on Mauna Loa only indicates that specific region’s endogenous concentration (ie. CO2 is NOT very well mixed), or
2) Their has been a HUGE increase in a SOURCE of naturally occuring carbonic acid being added to the ocean (ORDERS of magnitude greater than what man has added by burning fossil fuels), or
3) Their has been a HUGE loss of a natural active SINK that would normally sequester atmospheric CO2.
4) Or of course, a little of ALL OF THE ABOVE.
My bet is that the loss of huge areas of the Amazon rainforest has caused #3. The result will be that crops/other plants/the ocean will respond and the rest of the earth will continue to green.

fred

Every time I exhale my eyes burn and my teeth dissolve. Soon there will be nothing left of me.

Gail Combs

The are a couple other things that are left out of the topic of ‘ocean acidification’
The first is volcanoes:
Thousand of new volcanoes revealed beneath the waves
Giant Underwater Volcanoes Discovered
Volcanoes not only spew CO2, they also produce 36 million tons of chlorine a year and HCl is a strong acid compared to H2CO3. link Then there are the other gases… The most abundant gas typically released into the atmosphere from volcanic systems is water vapor (H2O), followed by carbon dioxide (CO2) and sulfur dioxide (SO2). Volcanoes also release smaller amounts of others gases, including hydrogen sulfide (H2S), hydrogen (H2), carbon monoxide (CO), hydrogen chloride (HCL), hydrogen fluoride (HF), and helium (He).
The second is organic acids:
I dealt with two different DI water systems fed with river water. One in NH (1980s) and one in NC (2000). The pH varied depending on whether or not we had a lot of rain. Abundant rainfall meant the pH stayed in a reasonable range (slightly acidic), Drought meant we got organic sludge full of organic acids and the pH fluctuated wildly messing up the chemistry of our production batches. I titrated samples of that deionized river water every day at a minimum and the amount of KOH needed to make each batch slightly alkaline was never the same. (If you have ever had to change DI water filters you will never ever drink city water again.)
Now think of that ever changing organic soup we call oceans. If the pH stays close to 8.1 to 8.2 despite this very dynamic system, a few ppm change in atmospheric CO2 isn’t going to mean diddle-squat.

Gail Combs

Kasuha says: @ July 8, 2013 at 10:32 pm
When you’re standing near the South pole and go away from it, you may insist that you’re becoming less southward but you are still going North. It’s just a wordplay with no practical meaning because your motion doesn’t depend on how you call it…..
>>>>>>>>>>>>>>>>>>>>>>>>
You are not a chemist. Every time I see a label proclaiming “Chemical Free” I am tempted to ask if they are selling a container of absolute vacuum. Every time I hear someone say they have a throroughbred Labrador Retriever or whatever, I want to ask what race horse was the sire and how in Hades they managed to get a cross….
Precise language counts and the debasement of language is the refuge of scoundrels.

Henry Keswick

Not an easy read at 7:00am (UK time) but it was worth sticking with it – a quite superb article, one of the best I’ve read here.
This article and its conclusions would serve as basis for an excellent and informative TV programme (along the lines of Horizon on the BBC for example).
Sadly I suspect that none of the valid points raised by you will make it to the airways anytime soon and certainly not via our biased state broadcaster which stopped doing proper science years ago.

Keitho

When the whole AGW thing fired up we were unprepared and lacked focus so the MSM and political scientists and politicians were up and running and held the public’s imagination. The run up to Copenhagen and Climategate got a lot of people off their bums and busy learning so the AGW supertanker took some time to slow and begin to turn. We still have the hysterics like WtD but they are fighting a forlorn rearguard action egged on by a few bitter enders but they have less and less relevance.
Today we are many and we have focus and more importantly we communicate constantly thanks to the Internet. The OA story is being challenged and squashed thanks to our focus and articles like this one are totally excellent in that it is clear and cogent and accurate. Thanks Steve, and Anthony for putting it up.

Gail Combs

DonV says….
Uniform in the atmosphere is an assumption that is necessary for CAGW. see: link you can look at different months and the averaging of large samples.
Mauna Loa Data gathering step 4:

4. In keeping with the requirement that CO2 in background air should be steady, we apply a general “outlier rejection” step, in which we fit a curve to the preliminary daily means for each day calculated from the hours surviving step 1 and 2, and not including times with upslope winds. All hourly averages that are further than two standard deviations, calculated for every day, away from the fitted curve (“outliers”) are rejected. This step is iterated until no more rejections occur.
http://www.esrl.noaa.gov/gmd/ccgg/about/co2_measurements.html

In other words they toss out any data that does not meet their preconception.
Illustration:
Graph: Raw hourly data
Graph: after manipulation of the data

Janice Moore

“Precise language counts and the debasement of language is the refuge of scoundrels.” [Gail Combs at 11:48PM]
Yes! It makes me shake my head (at the very least — usually, I say something precise, heh, heh) every time I hear a TV ad say “and no nasty chemicals” (or the like). For crying out loud!
I was pleased to see (far above) that you weighed in here, Ms. Combs. I thought of you (and some others, but especially you) as I read Mr. Burnett’s fine article and thought, “I hope Gail Combs responds,” — and you did.
You and George Orwell, great minds….
“Vague and imprecise language is no accident;
it is a conscious attempt to distort and deceive.”
[quoted from memory, only]
And, re: “less alkaline” it is very important to use precise language, for the key fact thus made clear (to all but the dullest among us) is: the oceans are STILL ALKALINE.

New paper finds prior claims about effects of ocean “acidification” may be overblown
http://hockeyschtick.blogspot.com/2013/05/new-paper-finds-prior-claims-about.html
SPPI paper on Ocean Acidification
http://hockeyschtick.blogspot.com/2010/05/new-sppi-paper-on-ocean-acidification.html
New paper unexpectedly finds CO2 and ‘acidification’ dramatically improved fish reproduction
http://hockeyschtick.blogspot.com/2013/05/new-paper-unexpectedly-finds-co2-and.html
New paper finds resilience of shelled plankton to ocean ‘acidification’, ‘suggests the future of ocean life may not be so bleak’
http://hockeyschtick.blogspot.com/2013/04/new-paper-finds-resilience-of-shelled.html
New paper discovers a ‘major source’ of alkalinity that might protect reefs from ‘acidification’
http://hockeyschtick.blogspot.com/2013/04/new-paper-discovers-major-source-of.html
New paper finds no evidence of ocean ‘acidification’ in upper Santa Monica Bay
http://hockeyschtick.blogspot.com/2013/06/new-paper-finds-no-evidence-of-ocean.html
New study finds reef fish can rapidly adapt to climate change within 2 generations
http://hockeyschtick.blogspot.com/2012/07/new-study-finds-reef-fish-can-rapidly.html
and others…
http://hockeyschtick.blogspot.com/search?q=acidification

dudleyhorscroft

higley7 says:
July 8, 2013 at 10:35 pm
4. If nothing unusual is happening, then what is the problem?
There is no problem other than keeping politicians so scared about CAGW that they keep on giving you grants to keep people scared about the ‘problem’.

michael hart

Ryan says:
July 8, 2013 at 8:22 pm
“10. The organisms most susceptible to ocean acidification from CO2 evolved at a time when concentrations were 15 times higher than today.”
No they didn’t lol. Their ancestors did. The species alive today have not contended with 500+ ppm CO2 in a LONG time. And they experienced massive die-offs at all classification levels during rapidly-shifting atmospheric gas levels. Geologically rapid that is, which is usually slow compared to the speed we are releasing CO2.

Ryan, at the individual level, even you contain DNA that evolved hundreds of millions of years ago. Like many simpler species there is a lot of DNA that you are not actively using at any given moment. In fact I sometimes suspect that you are finding new ways to not use it.
Be that as it may, experiments have demonstrated examples of bacterial resistance to antibiotics where, once acquired, resistance is not lost even in the absence of the selecting antibiotic. Gross generalizations are perilous. The ‘oceanic genome’ is incredibly complex, a system of powerfully adaptive organisms and awesome diversity.