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.
For those interested in further explorations of the oceanic pH, CO2 system, there’s a very good calculator for Excel, called CO2sys:
http://cdiac.ornl.gov/oceans/co2rprt.html
A good starting point is 35 parts per thousand salinity, 2200 uM alkalinity, and the pCO2 of your choice (in ppmv).
No discussion of ocean acidification would be complete without a discussion of alkalinity, a simple chemical variable that in effect measures the buffering capacity.
1. The oceans are acidifying.
<<<<<<<<<<<<<<<<<<<<<<<>>>>>>>>>>>>>>>>>>>>
Balderdash, as your post goes on to show. Why do you repeat alarmist propaganda as the truth, when you know better? A little more good, old-fashioned scientific rigor, please.
Also, aragonite and calcite, the two minerals of calcium carbonate have the same chemical formula but different properties, with different solubilties.
I agree with the comments above concerning precision of language. Sloppy expression gives the game away. Slight fluctuations in alkalinity is not, repeat not, acidification.
rgbatduke says:
July 8, 2013 at 9:49 pm
Willis Eschenbach says:
July 9, 2013 at 3:32 am
Notwithstanding the always interesting and germane critiques raised by the above, please cut Steve some slack on the details. He has made a chemical engineer’s overview analysis of the gross limiting aspects of the potential for disastrous acidification of the oceans given the nature of buffering mechanisms in the ocean, with some small mention of the work of organisms. Your remarks do make a definite contribution, as do others who look at the geological record of the abundance of shells and reefs living during times of 4000ppm CO2, but I think Steve intended to present at a very fundamental level, much like I have seen Willis and rgb make use of “black-body” radiation and Stefan–Boltzmann constant, etc., even though there are miriad other effects that fog up the picture. He also suggests lab experiments to assay different CO2 levels, resulting pH changes and the effects on living shells, etc – except for clownish experiments using acetic acid to dissolve shells and the like, such careful experiments, for some reason do not seem to be done by climatologists who are worrying about the issue: his FAQ
“9. The experimental framework for testing carbonate organisms with increasing CO2 is easy, yet unperformed”
I think demonstrates again the assertion-type “science”, as opposed to the empirical, that seems to satisfy climate scientists of the CAGW camp. I take away the following: it doesn’t eliminate all potential concerns, but it does convince me that losing sleep over disastrous pH change in the oceans is at least one heck of a way off. It also tells me that if the alarm has been raised because of acetic acid experiments, then the issue is even farther off than a heck of a way off.
Latitude says: @ur momisugly July 9, 2013 at 5:49 am
…. Steve, lots of studies….same results
As CO2 increases, production increases…
Most studies compare apples to oranges though….organisms that get their calcium/carbonates from the water…..and ones that get it from their food
All the studies really do is show which organisms stop growing when Ca/Mg/etc is not available…..duh!……
>>>>>>>>>>>>>>>>>>>>>
I know nothing of ocean organisms aside from raising fresh water fish as a kid, however I do know that if you mess up the Ca/Mg/P ratio in young horses (feed too much alfalfa hay without balancing it with grain) you really really mess-up their bones. Photo of a hoof showing inbalance from link
This means that unless the researchers know everything about the care and feeding of the sea life they are studying in a lab setting, they can attribute to CO2 results from an imbalance that would not occur in the ocean, and as I said before I doubt they duplicate the ocean basin (lithosphere) in the lab.
bob droege says:
July 9, 2013 at 9:56 am
Sometimes Wiki can be a good place to start
…..Basically, with lower pH in the water, Ca++ becomes more soluble and calcium carbonate shells are harder for the little beasties to form.
>>>>>>>>>>>>>>>>>>>>
And sometime wiki is not especially given Wikipedia climate fiddler William Connolley
I suggest you study the subject of buffers indepth. Here is a place to start that explains why Wiki is too simplified and lies by omission.
Gail Combs says:
July 9, 2013 at 10:40 am
I know nothing of ocean organisms aside from raising fresh water fish as a kid, however I do know that if you mess up the Ca/Mg/P ratio in young horses (feed too much alfalfa hay without balancing it with grain) you really really mess-up their bones. Photo of a hoof showing inbalance from link
This means that unless the researchers know everything about the care and feeding of the sea life they are studying in a lab setting, they can attribute to CO2 results from an imbalance that would not occur in the ocean, and as I said before I doubt they duplicate the ocean basin (lithosphere) in the lab.
=====================================================================
Good points, but I would add that in properly designed tests, control groups should mitigate test design flaws.
HOWEVER, the Mendelian Fudge Factor could come into play.
Steve Burnett
Overall an excellent well written piece that accomplishes the goal of discrediting alarmist concerns like those found in the youtube video. However, the more scientifically sound literature is more concerned with (super)saturation state and saturation depth claiming that calcifying rates decrease even with decreasing super-saturation states in organisms. In other words, according to them (and the papers they cite) whether the seawater is at 200% saturation or 300% saturation makes a difference to calcifying organisms.
http://www.pmel.noaa.gov/pubs/outstand/feel2633/feel2633.shtml
The linked publication is hardly free from error. In their figure 1 (and throughout the publication) they equate pCO2 (seawater) with pCO2 (atmosphere) without regard to Henry’s Law. They also fail to notice that aragonite vs. calcite forming organisms are already distributed globally in such a way as to minimize the impact of rising sea temperatures. They don’t seem to think it’s important to consider any upward shift in saturation depth would bring unsaturated seawater into contact with previously deposited calcium carbonates. Of course, they don’t really get into the biosphere feedbacks either; Willis has posted on that: http://wattsupwiththat.com/2011/10/25/the-reef-abides/
Suffice it to say there are a myriad of reasons why even an avid surf fisherman like myself needn’t worry about “ocean acidification” (argh, I still hate that technically correct but misleading phrase) and you covered quite a few of them quite well. You’re definitely right that this issue is their proverbial ace up the sleeve and we should be prepared for them to use it more as the “warming” isn’t cooperating and extreme event wallowing will get old eventually too.
Well said, Gail Combs.
While much of Wikipedia may still be relatively free of overt political corrections, I can no longer trust that simple chemistry pages about pH will remain free of the ‘William Connelley’ touch from one day to the next.
But it was always inevitable from the start. Every civilization falls. Eventually. Some sooner than others. When Wikipedia historians want to know the causes of the beginning of the end, then they have at least one name to start with…
Hi folks there are some phenomenal questions here and I would really like to address them all. It is however its a bit difficult to achieve the personal touch through this thread. If you have any other questions, critiques, praise or hate mail you can throw it at me through linked in. I’m pretty sure that’s a shameless self promotion but its really done with the best of intentions.
http://www.linkedin.com/in/stburnett/
Just a couple of notes
First someone a couple people have pointed out my equation 6 is … well off. I believe you are correct.
unbalanced:
Ca++ + CO3– + H+ –> 8.199 can occur with an increase in pCO2 in the atmosphere of 30%. This change however small would still be a form of acidification, however at the same time the solution would simultaneously be increasing its alkalinity, and any future acids would be buffered accordingly. This is why I was saying pH is irrelevant in a carbonic acid/carbonate context.
Outstanding read for a non-scientist with a basic understanding of chemistry (one College course). Hope someone hires you very soon.
I enjoyed Willis Eschenbach’s graphs of seawater pH changes – real data, real measurements.
Thank you!
A simple crucial experiment proposal:
-Take real open sea surface water (not fresh water, preferably not coastal seawater).
-Filter it by 0.5 micrometer filter (to get it rid of bacteria which could spoil the results) and/or sterilize it in airtight container.
– Cool it to 16.7 C.
-Measure the water pH.
-Cool the water in place with controlled temperature 16 C where you put it (optionally on ultrasonic/magnetic stirrer to accelerate the reactions) in container avoiding contact of the water with the surrounding air (a simple flask with 1-tube in/1-out will do the job) and let 280 ppm CO2 air (a mix of 78.09% nitrogen, 20.952% oxygen, 0.93% argon and 0.028% CO2 – air with appropriate part of CO2 freezed out) bubble through water for some time (hours).
-Then take sample and measure the water pH.
-Then take the same seawater warm it back to 16.7 C and let ~400 ppm CO2 air bubble through it.
-Again take sample and measure the water pH.
-Repeat or do simultaneously with at least 4 samples.
-Average the results, compare.
(-of course one can do the experiment with more than two steps of the CO2 concentration)
I would think such a simple experiment (doable in any standard chemical lab) can put to rest the longlasting academic disputes whether the CO2 elevated levels in the atmosphere can overcome the buffer and actually cause significant seawater acidification or not.
I don’t care about the acidification argument, but I care about calcium carbonate, and I’d like to contradict that part with a simple experiment:
Take a bit of powdered chalk (calcium carbonate), give it into your choice of water and bubble your breath (enriched with carbon dioxide) through it with a straw. (This will mimic higher levels of carbon dixoide). After a while, the calcium carbonate WILL dissolve to soluble calcium hydrogen carbonate (or calcium bicarbonate). [I suggest you try that yourself.]
I suspect you forgot the comproportionation of carbonate and carbonic acid to hydrogen carbonate at the given pH.
If the carbon dioxide concentration in the atmosphere increases, the one in water will increase along (Henry’s Law), and along goes the carbonic acid concentration. For every mole of carbonic acid (44 g), you will dissolve a mole of calcium carbonate (100 g).
It’s not a concentration thing, it’s an amount thing.
Dustin,
The issue frankly is not that simple. The problem with a beaker filled with chalk and continuous CO2 being added is you can replicate the same effect at any atmospheric concentration of CO2 it simply takes longer to dissolve.
In order to prove harm we need to know whether or not carbonate is the limiting reactant for calcium carbonate reactions. You would also need a near continuous feed into your system from other calcium carbonate sources.
Experiments done with constrained systems, having no Ion exchange prove nothing more than continuously dissolving CO2 will eventually dissolve a carbonate shell. It tells us nothing about live creatures responding to such circumstance,
So the question isnt will calcium carbonate dissolve its will all of it dissolve. Try performing the same experiment with a glass half filled with chalk powder, such that not only is the water saturated but there is a substantial layer on the bottom are you able to blow enough air into that glass to dissolve the half full glass of Ca CO3? are you able to do the same thing with a stir bar in the glass that is half full? If either of those show complete dissolution then there is no level of CO2 which wouldn’t cause complete dissolution eventually. If it doesn’t all dissolve then that would entirely nullify the ocean acidification hypothesis as clearly Ca solubility is a factor.
The problem with these experiments as attempts to validate ocean acidification is both outcomes essentially nullify the hypothesis, one outcome nullifies CO2 concentration as the problem, the other nullifies that its a problem at all. IT simply proves that the experiment is not a valid test of the ocean acidification hypothesis
Aren’t there the Carbonate compensation depths under the so called lysocline? Isn’t the solubility rates of Calcium carbonates rising over their formation rates only at a quite high pressures and low temperatures at relatively very high depths of several kilometers? Isn’t this basics of basics of the ocean chemistry the NOAA administrators should know by heart? Aren’t the calcium carbonates practically insoluble in the basic sea surface water and what the madam shows in the video with the chalk, fresh water and acetic acid in it isn’t it basically a severe scientific misconduct if she suggests it has something practical to do with the living pteropod shells dissolution purportedly due to rising CO2 levels in the atmosphere? Aren’t the pteropods and most of the calcifying organisms living mostly way above the lysocline and calcite saturation horizon?
Which brings me to a rhetorical question: Isn’t the video and it’s dissemination, especially at the official NOAA YT channel, around the edge of a conduct called federal fraud (under USC 18 §1001 sec. a/2)?
Glad to see people weighing in on imprecise and misleading language use.
Thanks Gail Coombes, and others.
“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.”
Agreed!
To say ”more acidic” clearly implies that you consider the oceans are already acidic.
“More” means extra or an increased amount of anything you have already got or your start point. In this debate let’s be precise so no one misunderstands the issue.
The use of terminology such as ”more acidic” or ” oceans are acidifying” leads many people to believe they are already acidic and becoming more so, and will get to a stage where things dissolve.
Hence we have so much controversy, such disbelief when we try and discuss this subject with believers that that is happening.
It’s also terminology that alarmists are very happy to perpetuate because they know it has that scary effect on people.
We here need to be mindful that we make our job harder by also using such terminology.
It is incorrect, imprecise and implys the wrong impressions.
Great article though. loved it.
Very nice post. Steve repeated the claim that ocean acidity has increased by 30%, explained as follows, “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.”
However, acidity is defined quantitatively in terms of the amount of hydroxide ion that can be titrated with the solution in question. While true that the very low concentration of H+ increased by 30%, the concentration of bicarbonate ion, at much higher concentration, determines how much hydroxide is neutralized. It increases by only a few % in sea water. The definition of acidity is being used incorrectly to exaggerate this “acidification.”
Interestingly, H+ in sea water is not constant and varies naturally by 500 to 1000%.
Doesn’t a dissolution of CaCO3 actually rise alkalinity by adding the CO3– (cappable to absorb two H+ ions)?
Does the addition (or removal) of CO2 to a solution change the alkalinity? Isn’t the answer No? Isn’t it because the net reaction produces the same number of equivalents of positively contributing species (H+) as negative contributing species (HCO3- and/or CO3–)?
Just asking.
OK Gail,
I looked again at wikepedia and could not see any evidence that William M. Connolley edited that page, and I checked the William M. Connolly page and found that William M. Connolley had edited his own page.
Then there is this, seems rather neutral on the global warming subject
http://ion.chem.usu.edu/~sbialkow/Classes/3600/alpha/alpha3.html
Shows a increase in CaCO3 solubility with decrease in pH, same as wikepedia
And the page you cited is rather mute on the subject.
Or you could try it yourself, chaulk and acid are easy enough to come by.
tumetuestumefaisdubien1 says:
July 9, 2013 at 1:38 pm
I would think such a simple experiment (doable in any standard chemical lab) can put to rest the longlasting academic disputes whether the CO2 elevated levels in the atmosphere can overcome the buffer and actually cause significant seawater acidification or not.
========
No, because there is a huge reservoir of precipitated salts in the form of limestone and similar rocks that will reenter the solution to prevent any attempt to overcome the buffer.
Isn’t the dissolution of CO2 in water actually exothermic with enthalpy of solution (moreover dependent on temperature) like ~ -20 kJ/mol? (Just absolutely btw. to put it in the perspective – isn’t the 20 kJ/mol equivalent of energy needed to warm one mol CO2 541 K?)
CO2 with human characteristics? That’s a new one!
ferd berple says:
July 9, 2013 at 6:19 pm
“No, because there is a huge reservoir of precipitated salts in the form of limestone and similar rocks that will reenter the solution to prevent any attempt to overcome the buffer.”
I would guess so, but wouldn’t it be nice to confirm this with experiment to put the ocean acidification hype to rest?
Robert Landreth says:
July 9, 2013 at 9:37 am
The Permian basin has thousands of feet of Dolomite formed during the period for which it was named.
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add in subduction and you have the following:
dolomite + water + iron + heat + pressure —-> hydrocarbons (oil/gas) + rock