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.
Jennifer Marohasy BSc PhD is a critical thinker with expertise in the scientific method.
Temperature fluctuates ‘orbitally’ depending on the progressional and differing terrestrial geographical parameters of the Solar-induced Orbital Dry Cycle Hierarchies.
‘The Temperature/Precipitation Paradox;
As the expelled Solar Particles interact with and remove/convert Water Vapor Albedo in the Earth’s upper atmosphere – there is a resultant increase in temperature via the commensurate increase in Solar Energy reaching the Earth’s surface. This increase in temperature over the various land masses under the orbiting Dry Cycle Canopy, results in increased evaporation but reduced precipitation,(due to the reduced Water Vapor Albedo) over these areas, with the likely consequence of developing Drought conditions over these affected land masses.
However, the associated increase in temperature over various substantial water-bodies (Oceans/Seas/Lakes,) under the Dry Cycle Canopy, results in increased evaporation and precipitation tendencies over these areas as well. These resultant storm-prone regions, are especially significant near the Dry Cycle vanguard, which is moving East to West at half a degree of Longitude per Day/Night Interval – and confronts the prevailing weather patterns moving West to East (and towards the Poles,) due to the Earth’s Axial Spin. These ‘conflicting’ forces however, do not prevent the overall reduction in precipitation over land and water, that the Solar-induced Orbital Dry Cycle brings.
The Oceans certainly represent key factors in the transfer of temperature and precipitation around the globe – including the mechanisms of heat transfer and convection – though the primary instigator of Temperature and Precipitation control at the Earth’s surface, is the immutable Dry Cycle Frequencies over time, that result in expulsion of charged particles from the Sun, which in turn leads to the alteration/conversion of Water Vapor Albedo,(Reflectivity) in the upper atmosphere – and subsequent Temperature rises under the resultant Orbital Dry Cycle Canopy.
It should be noted that other sources of Albedo,(such as Sea and Land Ice, Ocean reflectivity, wind-blown dust and Volcanism,) also affect Temperature and Precipitation – and remain important factors in the overall ‘cooling’ of the climate.
(see ‘The influence of ‘Albedo’ on the ‘Dry’ Cycles’, p 129).’
‘Tomorrow’s Weather’ – thirty years on….(p361)
“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.”
Le Chatelier’s Principle is a simple consequence of the second law of thermodynamics. It is important, though it does not give us as much as we might like for our work.
It is a principle of classical thermodynamics. For the Principle to apply, the “balance” mentioned above must be with all flows being zero, not just a net balance amongst various flows. Not mentioned above, and usually only implicit in statements of it, is that the Le Chatelier Principle needs the participation of a variable that can ‘leak’ away some effect of the primary perturbation. Without the ‘leak’, the Principle has nothing to say.
When there are non-zero flows, the Principle does not necessarily apply. For example, it does not apply under all conditions to the very important industrial Haber process, because there are substantial flows in the Haber process.
When he was in Melbourne, the great and admirable Will Happer proposed to justify his argument of negative feedback by invoking the Le Chatelier Principle. But that wasn’t a proper justification, because the earth’s energy transport process involves many substantial flows. Other arguments are necessary to justify its negative feedback. Such other arguments are valid, and negative feedback applies to it, but not because of the Le Chatelier Principle.
It is a colourful metaphor, used by many respectable persons, but it is only metaphorical to say that ‘the system tries to’ do things. I think it wise to avoid that metaphor. (Technically, it is a version of what known as the ‘pathetic fallacy’, attributing animal feeling and will to inanimate things.) There is no general principle that things ‘try to stabilize’, beyond the fact that stable states tend to persist, while unstable states are transients between stable states. Stability and instability are to be judged on their respective merits.
The ocean’s CO2 flows are substantial, so that, in general, the Le Chatelier Principle does not apply to them. In most scenarios, they exhibit negative feedback, but further arguments are necessary to prove that.
Christopher Game,
Le Chatelier’s principle is not limited to thermodynamics and is not limited to static equilibria as you described, that is, all flows need not be zero.
Le Chatelier’s principle, when applied to the dynamic equilibrium of atmospheric CO2 concentration above seawater, describes how the system responds to perturbations by counteracting those perturbations with changes to restore balance. In the context of the ocean-atmosphere interface, CO2 exists in a dynamic equilibrium governed by Henry’s law, where the net flux of CO2 is the result of simultaneous emission from the ocean surface to the atmosphere and absorption from the atmosphere into the ocean. A disturbance, such as a change in temperature or partial pressure of CO2 added to air by humans, prompts the system to adjust in a way that mitigates the perturbation. For instance, a decrease in sea surface temperature increases CO2 solubility in the surface ( assuming all other variables unchanged), decreasing CO2 outgassing and increasing CO2 absorption, which temporarily lowers atmospheric CO2 concentration in air. This dynamic interplay ensures the system resists abrupt shifts, maintaining a relatively stable net flux despite opposing fluxes. Flux is the mass of material that moves through a surface in a unit of time.
The 1991 eruption of Mount Pinatubo provides a clear example of this principle in action. The eruption injected aerosols and clouds into the stratosphere, reducing insolation over tropical oceans and cooling sea surface temperatures. This perturbation disrupted the Henry’s law equilibrium partition ratio, enhancing CO2 absorption into the cooler ocean and leading to a sharp decline in atmospheric CO2 concentration for approximately two years, as evidenced by the negative second derivative of CO2 levels in NOAA Mauna Loa data. However, as the aerosols dissipated and sea surface temperatures recovered, the system responded per Le Chatelier’s principle: the equilibrium partition ratio of CO2 aqueous/CO2 gas which had been rapidly decelerating for 2 years post eruption abruptly reversed to acceleration, with CO2 outgassing accelerating rapidly. About four years post-eruption, the atmospheric CO2 growth rate not only recovered but exceeded the pre-eruption slope, effectively catching up to the expected global trend as if the perturbation had not occurred. This illustrates how dynamic phase-state equilibria, like the ocean-atmosphere CO2 exchange, adapt to disturbances by balancing opposing fluxes to stabilize the net system behavior.
In the context of Le Chatelier’s principle, a “leak” refers to a pathway or mechanism that allows the system to counteract a disturbance, effectively “leaking” the imposed stress to restore equilibrium. For the dynamic equilibrium of atmospheric CO2 above seawater, a “leak” could describe processes that mitigate deviations from the equilibrium state, such as enhanced CO2 absorption or emission fluxes responding to perturbations like temperature or concentration changes. In the case of the 1991 Pinatubo eruption, the initial cooling of sea surface temperatures increased CO2 solubility, acting as a “leak” by drawing more CO2 into the ocean, reducing atmospheric levels for about two years.
The rapid recovery to the pre-Pinatubo CO2 growth rate, a 2 year acceleration following a two-year deceleration, can be framed as a manifestation of this “leak.” As the aerosol-induced cooling dissipated and sea surface temperatures warmed, the system’s response—accelerated CO2 outgassing—served as a counteracting flux to restore the pre-eruption equilibrium trajectory. This swift rebound, overshooting to catch up with the expected global CO2 slope, reflects the dynamic equilibrium leveraging the “leak” of increased ocean-to-atmosphere CO2 flux to offset the earlier suppression, aligning with Le Chatelier’s principle’s drive to minimize disruptions.
Fick’s Law helps to overcome the limitations of Henry’s I Law in large areas of upwelling or downwelling.
I have made the point several times without previously being aware of Fick’s Law.
Bud Bromley says: April 14, 2025 at 4:28 pm
“Le Chatelier’s principle is not limited to thermodynamics and is not limited to static equilibria as you described, that is, all flows need not be zero.Le Chatelier’s principle is not limited to thermodynamics and is not limited to static equilibria as you described, that is, all flows need not be zero.”
Thank you for your response. In cherry picked cases, one may extend Le Chatelier’s Principle beyond thermodynamics, and extend it beyond static equilibria, and certainly it will appear sometimes to apply when all flows are non-zero. But such extensions are not Le Chatelier’s Principle. They are ad hoc, cherry picked extensions of it. Le Chatelier’s Principle is rigorously correct within its proper domain of applicability, as for thermodynamics in general. As with thermodynamics, beyond its domain of proper applicability, it does not supply valid argument.
You may find plenty of negative feedback stable dynamical scenarios, and you may say that they are predicted by Le Chatelier’s Principle. But Jennifer is looking for reliable valid reasoning. Le Chatelier’s Principle can be relied upon as an argument when it is applied within its proper domain of applicability. But beyond its domain of proper applicability, it does not provide reliable valid reasoning. A case of a superficial appearance that it applies beyond its domain of applicability is just that: a case of superficial appearance, that is not a valid step of reasoning.
I suggest I. Prigogine & R. Defay, ‘Chemical Thermodynamics’, translated and revised in conjunction with the authors by D.H. Everett, Longmans Green & Co, London, New York, Toronto, 1954 (originally in French published by Desoer Editions, Liege, Belgium), for a good discussion.
There are sound arguments for demonstrating stable steady states and suchlike, and they are to be marshalled for our purposes. But we would damage our own credibility by invoking Le Chatelier’s Principle when it does not apply. Instead, we need to provide valid arguments.
“… aligning with Le Chatelier’s principle’s drive to minimize disruptions.” In logic, this metaphor is known as the ‘pathetic fallacy’, attributing will or drive to an inanimate process.
Hi Jennifer,
Well, I didn’t intend to comment any longer, but just 2 items for your consideration:
1. What about Clausius-Clapeyron? I see it mentioned multiple times in climate discussions…
2. Climate “science” introduced a new kind of metric: Temperature increase as result of a doubling of atmospheric CO2 concentration.
Could you translate your chemistry laws into similar metrics: what will be the CO2 increase in earth”s atmosphere as a result of a 1/10/100% change in the conditions your laws are applied to*.
* I raised this question during the Ivan Kennedy zoom meeting, but didn’t get an answer…
This is well above my pay grade, but a recent paper might throw some light on the issue.
https://notrickszone.com/2025/04/14/new-study-finds-the-anthropogenic-pressure-on-climate-is-too-small-to-play-a-dominant-role/
Bud Bromley says: April 14, 2025 at 4:28 pm
“The 1991 eruption of Mount Pinatubo provides a clear example of this principle in action.”
It might superficially appear that this is an example of Le Chatelier’s Principle in action. But such an appearance is spurious. The eruption of Mount Pinatubo is an example of a kind of dynamic stability, but not of Le Chatelier’s Principle in action.
There are big differences between the dynamically stable states in general, and stable stationary states that are covered by Le Chatelier’s Principle. Study of the stability of dynamical systems in general is not child’s play. This is because, in general, dynamical systems operate under several or even many time scales. In this light, Le Chatelier’s Principle is the extreme simplest case, in which the dynamical aspect has settled, and the time scale has disappeared, or has stretched to eternity, whichever you please. Study of stability under dynamic conditions demands careful specification of what time scales one is interested in.
The earth’s energy transport process has constituent mechanisms that go very fast, such as the radiative effects of added CO2, as well as a big range of slower processes, such as evaporation, and planetary orbital changes. Volcanic effects involve processes that take months or years.
For dynamical systems in general, it is not so simple to define ‘stability’. For example, how does one consider the ‘stability’ of a dynamically chaotic system? In important ways, the earth’s energy transport process is dynamically chaotic.