Before climate science became 'settled science', there were various theories suggesting that because the amount of carbon dissolved in the Earth's oceans exceeds that in the atmosphere by about a factor of 60, the atmospheric CO₂ content is dictated by the chemical state of the oceans. (I'm thinking of the work of W.S.Broecker and others.)
I'm working towards a New Theory of Climate Resilience, self funded at the moment. I've been reading Broecker's 'The Glacial World According to Wally' which provides some details that fits neatly with Alex Pope's own theory of glaciation that is often buzzing in the back of my mind.
I know that some consider me to be proceeding at a glacial pace with all of this. (Thanks for your patience, Alex Pope.)
One plank of my new theory, that I have been exploring with Ivan Kennedy, is the Thermal Acid Calcification Hypothesis to explain the seasonal patterns of atmospheric carbon dioxide concentration as measured at Mauna Loa, Hawaii. In proposing this, I have come to realise that many colleagues and friends have very little understand of the five key laws of chemistry that will affect the equilibrium potentially reached between a gas and liquid, think atmosphere and oceans. (Thanks to John Abbot for explaining them to me over the years.)
Others are perplexed that I care at all about atmospheric levels of carbon dioxide. For sure carbon dioxide may not be a driver of climate change, but its varying atmospheric concentrations tend to follow temperate change that is relevant to understanding climate resilience.
I have a zoom webinar coming up with Bud Bromley and while Bud could spend the entire hour explaining ocean chemistry, he doesn't want to. He wants to talk about more fun things, and I have promised that this webinar will be fun.
So, I am attempting to provide some background information in this blog post, useful background information perhaps to understanding ocean chemistry that will be relevant to my conversation with Bud that may focus more on volcanic eruptions, uncertain carbon budgets, and even misunderstandings about how atmospheric levels of carbon dioxide are measured at Mauna Lao, Hawaii.
Thanks to Grok, created by xAI, for the clear explanations of each of five important laws and one principle, which I’m excited to share below.
These laws, and the one principle, help unpack how CO₂ might move from the ocean to the air (and even back again), if there has been ocean warming from whatever cause since at least the 1950s. Grok has included the formulas as simply as possible for clarity. (Thanks Grok.)
1. Graham’s Law
Graham’s Law tells us how fast gases spread out or diffuse. It says that lighter gases move faster than heavier ones. The formula compares the diffusion rates of two gases based on their molar masses (M1 and M2):
Rate1 / Rate2 = sqrt(M2 / M1)
For CO₂ (molar mass 44 g/mol), this means it diffuses a bit slower than lighter gases like oxygen (32 g/mol). In my hypothesis, this law hints at how CO₂ moves from ocean water into the air, especially in choppy surface waters where gases mix. It’s a small piece of the puzzle, but it sets the stage for gas movement.
2. Ideal Gas Law
The Ideal Gas Law describes how gases behave under different conditions of pressure, volume, and temperature. It’s written as:
PV = nRT
Here, P is pressure, V is volume, n is the number of gas molecules (in moles), R is a constant (0.0821 L·atm/mol·K), and T is temperature (in Kelvin). For CO₂ in the atmosphere, this law helps us understand how its pressure changes as more CO₂ degasses from the ocean. If ocean warming (say, from circulation changes) pushes CO₂ into the air, this law tracks how that affects the atmosphere’s CO₂ levels.
3. Henry’s Law
Henry’s Law is key to understanding how much gas dissolves in a liquid, like CO₂ in seawater. It says the amount of gas dissolved is proportional to the pressure of that gas above the liquid:
C = k * P
C is the concentration of dissolved gas, P is the gas’s pressure in the air, and k is a constant that depends on the gas and temperature. If the ocean warms due to circulation shifts, k gets smaller, meaning less CO₂ stays dissolved, and more escapes to the atmosphere. This is central to my idea that ocean changes could drive CO₂ increases.
4. Fick’s Law
Fick’s Law explains how substances, like CO₂, move from areas of high concentration to low concentration. The formula is:
J = -D * (ΔC / Δx)
J is the flow of the substance, D is a diffusion constant, ΔC is the concentration difference, and Δx is the distance. In the ocean, if deep, CO₂-rich water rises to the surface (maybe from altered circulation), Fick’s Law says CO₂ will flow into the air where its concentration is lower. This could amplify degassing, especially in turbulent waters.
5. Law of Mass Action
The Law of Mass Action deals with chemical reactions that can go forward or backward, like CO₂ reacting with water to form carbonic acid and other compounds in the ocean. For a reaction like aA + bB cC + dD, it’s expressed as:
K = ([C]^c * [D]^d) / ([A]^a * [B]^b)
K is the equilibrium constant, and [X] means the concentration of each chemical. In seawater, CO₂ shifts between gas, acid, and ions (like bicarbonate). If more CO₂ enters surface water, this law shows how the balance tips, possibly pushing CO₂ back into the air. It’s a big part of the ocean’s CO₂ chemistry.
6. Le Chatelier’s Principle
Le Chatelier’s Principle says that if you disturb a balanced system, it adjusts to reduce that disturbance. No formula here, just a rule of thumb. For CO₂ in the ocean, if warming or extra CO₂ from deep water upsets the balance, the system tries to push CO₂ out to the atmosphere to stabilize. This principle ties all the others together, suggesting that ocean changes could naturally lead to more atmospheric CO₂.
According to Grok after my prompting, this matters because:
These laws weave together to explain how CO₂ might leave the ocean if circulation patterns, like the thermohaline system, have changed since the 1950s. Warmer water holds less CO₂ (Henry’s Law), concentration differences drive it to the air (Fick’s Law), chemical balances shift (Mass Action), and the system adjusts (Le Chatelier’s). The Ideal Gas Law tracks the atmospheric side, while Graham’s Law adds detail to gas movement.
The Zoom webinar, my interview with Bud Bromley, is in less than two weeks. Specifically we will be live at 6pm Hawaii time on Thursday, 24th April (2pm Brisbane-time the next day, Friday April 25th). This will be the fourth zoom meeting in my series Towards a New Theory of Climate Change. If you would like to be a part of this Webinar please register at:
https://us02web.zoom.us/webinar/register/WN_QrVa8XEzSPS_GvUWnXkX0Q
You will then be sent a confirmation email with a link that you will need to join the webinar, so please file the confirmation email carefully.
Bud lives in Hawaii and is a chemist by training.
The plan is that after the one hour interview, there will be another whole hour for questions, and comment. So, the plan is that Bud and I will be live for two hours with everyone who has registered unmuted for the second hour.
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The feature image is a photograph I took just this morning, at Lammermoor Beach, Yeppoon. There is so much bubble and foam at the beach at the moment with relatively acidic freshwater inflows.
Responding to Ivan Kennedy says April 30, 2025 at 9:02 pm
Thank you, Ivan, for your response. I repeat that I know nothing about this topic.
"First, the Keeling curve doesn’t show a flat zone corresponding to this temperature flatline period, you say is from radiosonde balloon measurements, I presume likely made on land."
I was reading the dataset collected by Ferenc Miskolczi, of about fifteen hundred radiosoundings, chosen to try to provide a global average. As you note, they are all landbased. We found a very small island, far from the mainland, in the Coral Sea, with radiosonde data, owned by Australia, but we didn't get around to analysing it: perhaps it may interest you?
I wouldn't describe the dataset's temperature trend from 1948 to 1977 as showing a flat zone. I would describe it as showing a definite downtrend over that time, though of course the data are noisy. So I would expect the Keeling curve to show a distinct downtrend over that time if it were driven mainly by present-time "global" temperature. With such meagre data, the timing would be hard to investigate.
Christopher, this is a worthwhile question you have mentioned, needing a rational answer.
My delay in answering has been because I've been out of reach of email since Monday.
First, the Keeling curve doesn't show a flat zone corresponding to this temperature flatline period, you say is from radiosonde balloon measurements, I presume likely made on land. However, Tom Quirk's analysis "The secrets of the Keeling curve" shows declining residuals before 1970, increasing after 1990,with bumps according to El Nino's. The TAC hypothesis is based mainly on seawater temperature variations affecting calcification, not that over land masses so global averages are irrelevant.
But the 1989 CO2 bubble followed a period of declining residuals, rising from about 1987.
In other words, Christopher there is more work to do to pin down causes and effects, but arithmetic has to be weighted by local environmental conditions it it is to be accurate.
Thanks for your observation. It needs to be better understood.
Ivan
Ivan Kennedy says April 27, 2025 at 10:05 pm
"Good questions. ... if you can."
Still above my pay grade. I get the impression that the calculations are not too easy? Does Noel have a degree of plausibility?
It worries me that the Keeling curve seems not to show the global average temperature fall from perhaps 1945 to 1977, as judged by radiosonde? Is that relevant?
Good questions. Remember that these numbers for emissions are arithmetic, with additive errors. Also, continuous emissions on land are also near photosynthetic ecosystems and may mix imperfectly, Rubisco fixing faster nearby. The increase in the atmosphere is more accurate, if you agree marine sites all over the globe give a better average estimate. Hardly anyone measures changes of pCO2 on land, it's just too variable, as Keeling found, to be reliable.
Trying to avoid arithmetic, we estimate quite accurately that each sq metre of the Earth's surface has 150 moles of CO2 above it, for a total area of 5.101x10e^14 m2. In 2021, we estimated 1.6 moles/m^2 of total emissions/yr, gradually mixing with the 150 moles in each column, a maximum 1% increase, though only an atmospheric increase of 0.7 moles m^2, about half this emission is observed. Our modelling indicated that up to half the emissions or 0.8 moles could be absorbed by each m^2 of the ocean with a similar increase taken up by accelerated photosynthesis, the so-called greening effect plainly seen from satellites. This suggests a 0.5% increase/yr in photosynthesis of a known mean value of some 35 moles m^2/yr, biased to land because of lack of nutrients in seawater. The pCO2 in air is close to the Km value of about 10-15 microM in water, so this can raise C-capture about 0.3%. Arid areas are much greener (Graeme Farquhar ANU Japan Prize and Australia Prize), and with a gradual 0.5% increase in pCO2 the water sparing effect for C3 plants with stomates less open could mean, using arithmetic the two processes might balance out.
We also know from seawater surface measurements that there is an increase of about 2 micromoles DissolvedInorganicCarbon/kg seawater/yr or 0.13 moles DIC/m^2 increase in the mixing zone of 65 m deep. We predict based on possible calcification of 0.7 moles of net acid calcification/m^2 that 0.7 moles of CO2/m^2/yr would produce an increase in atmospheric pCO2 of just over 2 ppmv. (Thanks for the small fine Christopher, for throwing in DIC).
So where do the emissions go? Current oceanographic measurements at ALOHA and elsewhere indicate that these absorptions are feasible and it may that such a balance is natural when global warming is absent and the seasonal effects balance out so Keeling Curve flatlines. At the moment is goes up 0.5% of the total level, or perhaps a little higher according to Bud Bromley. It is a variable regionally.
Unfortunately, I can't past our Figure 5 diagram here. Sorry to be so obtuse but it's a huge task to go global in arithmetic. We would prefer to concentrate on local measurements for predictions to subject to experiment.
Even if there were no fossil emissions (that just means no extra carbon is added annually to the global ecosystem), a continuing global warming would till cause increasing annual thermal acid-calcification and CO2 emission from surface seawater to the atmosphere. This is because each year the pH would fall and a higher concentration of CO2 in the atmosphere would be sustained. This would be like adding a shot of vinegar to your coke bottle or beer and replacing the cap.
Prove this wrong, if you can.
Noel Degrassi says April 27, 2025 at 1:16 pm
"The mass of CO2 in the atmosphere is going up by about 19 Gigatonne per year. The amount of CO2 released by burning fossil fuels is about 37GT per year. There seems to be an obvious conclusion from those facts.
It seems strange to posit that most of the 19GT is from the calcium carbonate equilibrium. Where does the fossil fuel 37GT go?"
Fair comment. This topic is above my paygrade, and I hardly know anything about it. Is there anyone who has other estimates of by how much the mass of CO2 in the atmosphere is going up each year, and of the amount of CO2 released by burning fossil fuels each year?
For Noel's comment to have more bite, we may ask how much CO2 is taken up by plants on the land each year?
Noel seems to be inviting us to conclude that a net 37Gt − 19Gt = 18Gt of fossil fuel burnings CO2 is absorbed by the sea each year.
The mass of CO2 in the atmosphere is going up by about 19 Gigatonne per year. The amount of CO2 released by burning fossil fuels is about 37GT per year. There seems to be an obvious conclusion from those facts.
It seems strange to posit that most of the 19GT is from the calcium carbonate equilibrium. Where does the fossil fuel 37GT go?