Guest essay by Jennifer Marohasy (reposted from her website by request) with addendum by Anthony.
Picture this: it’s a hot day, and you grab a soda can that’s been in the sun. You crack it open—psssht—and CO₂ fizzes out, tickling your nose, maybe spraying your shirt if you’re slow. It’s a tiny chaos, a burst you can’t control. Now imagine that fizz across the ocean’s sun-warmed surface, covering 71% of Earth, bubbling CO₂ into the air we breathe. Wild, right? A bit mad. I reckon it’s a missing piece of the climate puzzle.
The IPCC pins it all on smokestacks—11 billion tonnes of carbon a year from fossil fuels. Even skeptics like the CO₂ Coalition echo this, leaning on guys like Ferdinand Engelbeen who do their maths by the consensus numbers on this issue of CO₂ origins.
But they might have it all back to front and be leaving out ocean chemistry and biology. In fact, I’m convinced they are.
The Keeling Curve—CO₂’s climb from 280 to 420 ppm—carries their blame. But what if the ocean’s fizzing more than they think? Their rock-solid evidence could be mostly myth.
I’ve been digging into this with Ivan Kennedy, my second guest for the webinar series ‘Towards a New Theory of Climate Resilience’. That was back in February and I’m still to process the audio from this discussion.
Instead, my focus has been on writing technical papers. Ivan and I are working through a hypothesis that could perhaps flip the climate script.
Engelbeen claims fossil fuels’ isotopic fingerprint—light ¹²C (isotope C12) dragging the air’s ¹³C-to-¹²C ratio from -6.5‰ (per mille)* to -8.5‰ since 1850—is proof of coal and oil’s guilt. Ocean CO₂, averaging 0‰ from deep waters, should nudge it up—not down. Case closed.
Except. That ¹²C/¹³C tale’s shakier than they admit. What if the ocean’s surface, warmed by the sun, fizzes CO₂ richer in ¹²C than the deep oceans 0‰?
Calcification—limestone forming in seawater—might churn out CO₂ at -10‰ or lower, diluting that delta 13 signal just like fossil fuels. It’s not the deep ocean I’m on about—it’s the top 65 meters, the mixed layer, where sunlight and warmth cause biological action. So much action that it has built the biosphere’s great carbonate deposits, even the White Cliffs of Dover.
Ivan and I talked some of this over—Great Barrier Reef, North Pacific—during our webinar (soon my first podcast—thanks for waiting!). Calcification’s no sleepy trick; it’s a biological buzzsaw—corals, algae, phytoplankton like coccolithophores churning limestone. In summer blooms, they might pump out tonnes of CO₂, light on ¹³C. Our Thermal Acid Calcification (TAC) hypothesis says nature’s pitching in more than you might think.
Ponder this next time you sip a soda: could the ocean be bubbling up a CO₂ twist?
TAC’s perhaps a second plank in my New Theory of Climate Resilience. Subscribe for irregular updates, and to know about next webinars.
This is Part 2 of How Climate Works. Part 1 was with Bill Kininmonth. I never properly processed the audio from Part 1, and I accepted the AI summary of our meeting click here.
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When we say deep ocean carbon is 0‰ (per mille), we’re talking about its carbon isotope ratio, specifically the δ¹³C value. This is a measure of how much carbon-13 (¹³C) is present relative to carbon-12 (¹²C), compared to a standard reference.
In this case, 0‰ doesn’t mean there’s no carbon-13 in the deep ocean—it means the ratio of ¹³C to ¹²C in deep ocean dissolved inorganic carbon (DIC) is about the same as the standard reference, which is usually the Vienna Pee Dee Belemnite (VPDB). A δ¹³C of 0‰ indicates no enrichment or depletion of ¹³C relative to that standard.
Now, why is deep ocean carbon around 0‰? It’s because the deep ocean is a massive, well-mixed reservoir of carbon that’s been cycled through various processes over long timescales. Surface ocean carbon starts with a δ¹³C of about +1 to +2‰ due to photosynthesis, where phytoplankton preferentially take up ¹²C, leaving the surface water slightly enriched in ¹³C. But as organic matter sinks and decays, it releases carbon back into the deep ocean. This process, along with the mixing of water masses, balances out the isotopic signature. The deep ocean ends up with a δ¹³C close to 0‰ because it reflects a long-term average of all these inputs—biological, physical, and chemical—without much net fractionation.
In terms of carbon-13, this means the deep ocean has a pretty stable and “neutral” amount of ¹³C compared to the global carbon cycle. It’s not heavily skewed like surface waters or organic matter (which can be -20‰ or lower due to that photosynthetic preference for ¹²C). So, a δ¹³C of 0‰ tells us the deep ocean is kind of a baseline, a big pool where carbon isotopes have settled into equilibrium over thousands of years.
Addendum by Anthony: I was skeptical (gasp!) of Marohasy’s claims, so I decided to run it through Grok, but purposely asked the question in reverse of her premise, which I thought might prompt better results.. Grok does quite well with scientific questions. It seems to agree.
Marohasy states:
Except. That ¹²C/¹³C tale’s shakier than they admit. What if the ocean’s surface, warmed by the sun, fizzes CO₂ richer in ¹²C than the deep oceans 0‰?
The Grok response to this question is below:
Grok question:
On the ocean surface, does carbon dioxide with carbon 13 isotope come out of solution and into the atmosphere faster than carbon dioxide containing carbon 12 isotope?
Grok response:
Let’s dive into this intriguing question about carbon dioxide isotopologues—specifically, whether CO₂ with carbon-13 (¹³CO₂) comes out of solution and enters the atmosphere faster than CO₂ with carbon-12 (¹²CO₂) at the ocean surface. The process we’re examining is the outgassing of CO₂ from seawater into the air, and the key is to determine if the isotopic difference between ¹³C and ¹²C influences this rate.
The exchange of CO₂ between the ocean and atmosphere involves several steps: dissolved CO₂ must diffuse from the ocean’s bulk to the surface, cross the air-sea interface, and enter the gas phase. This process can be affected by both physical and chemical factors, including diffusion rates and reaction kinetics. Since ¹³C is heavier than ¹²C (atomic mass ~13 vs. ~12), we need to consider the kinetic isotope effect (KIE), where the mass difference can alter the speed of these processes.
First, let’s look at diffusion. In water, dissolved CO₂ moves toward the surface based on concentration gradients. According to Graham’s law of diffusion, the rate of diffusion is inversely proportional to the square root of the molecule’s mass. For ¹²CO₂ (molecular mass ~44) and ¹³CO₂ (molecular mass ~45), the difference is small, but ¹²CO₂ diffuses slightly faster because it’s lighter. The ratio of diffusion rates is roughly √(45/44) ≈ 1.011, meaning ¹²CO₂ moves about 1.1% faster than ¹³CO₂. This suggests that, all else being equal, ¹²CO₂ would reach the surface and outgas more quickly.
Next, there’s the chemistry. In seawater, CO₂ exists in equilibrium with carbonic acid (H₂CO₃), bicarbonate (HCO₃⁻), and carbonate (CO₃²⁻). The conversion of dissolved CO₂ to these species (and back) involves hydration/dehydration reactions, which can also exhibit a kinetic isotope effect. Because ¹³C forms slightly stronger bonds (due to its higher mass and lower vibrational frequency), reactions involving ¹³CO₂ tend to be slower. Experimental studies confirm that the hydration of ¹²CO₂ to bicarbonate is faster than for ¹³CO₂, meaning ¹²CO₂ is more readily available to outgas as it spends less time locked in these dissolved forms.
At the air-sea interface itself, the transfer of CO₂ into the atmosphere is driven by the partial pressure difference and turbulence, but isotopic fractionation can still occur. Research on gas exchange, including models and measurements of carbon isotope ratios (e.g., δ¹³C), shows that ¹²CO₂ is preferentially released into the atmosphere. This is partly because its faster diffusion and reaction kinetics give it an edge in escaping the ocean. The overall fractionation during outgassing enriches the atmosphere in ¹²C relative to ¹³C, leaving the ocean slightly enriched in ¹³C, as detailed in studies like those from NOAA’s Global Monitoring Laboratory.
So, does ¹³CO₂ come out of solution faster than ¹²CO₂? No, the opposite is true. Due to its heavier mass, ¹³CO₂ diffuses more slowly, reacts more sluggishly in seawater, and crosses into the atmosphere at a slightly lower rate than ¹²CO₂. The difference is subtle—on the order of a few percent—but consistent across physical and chemical processes. Therefore, carbon dioxide with carbon-12 outgasses into the atmosphere faster than carbon dioxide with carbon-13 at the ocean surface.
References
- Kinetic Isotope Effect – LibreTexts Chemistry
- Graham’s Law of Diffusion – Britannica
- Kinetic Isotope Effects in CO₂ Hydration – PNAS
- Carbon Isotope Measurements – NOAA Global Monitoring Laboratory
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Interesting suggestion. I recall an article here on WUWT that stated that the only reason that folks believe that C12 from burning hydrocarbons is the only source for atmospheric CO2 growth is because noone has looked for other sources.
It will be interesting to see how this hypothesis develops.
One did look at other sources and the other main source of low 13C, the biosphere is growing: the earth is greening, thus the biosphere is a net sink, not a net source, thus increasing the 13C/12C ratio in the atmosphere, no matter how much CO2 each (season or) year goes in and out.
The same for the oceans: the CO2 and derivatives (bicarbonates and carbonates) increased over time, at 10% of the increase in the atmosphere. That is the Revelle/buffer factor. Thus the ocean surface also is a net sink for CO2.
Human emissions are one-way into the atmosphere with (near) zero human sinks. Twice as high as the observed increase…
You overlook the fact that not all of the new growth sequesters CO2 mid-term. Leaves of deciduous trees, and annual plant detritus will be increasing, providing food for fungi and bacteria, which release CO2 all year long. Also, Boreal trees respire CO2 at night and in the Winter, releasing CO2 enriched in the more mobile 12C.
You also overlook the fact that little of the small plankton survives its transition to the abyssal plain, with the ‘plasma’ decomposed by bacteria and increasing the amount of 12C-enriched CO2, which should be increasing with increasing warmth and CO2.
You and others need to start looking at the seasonal changes in CO2, and not just focus on the net annual changes, for a better understanding of the processes. The draw-down Summer phase is shorter in duration than the ramp-up phase, and is limited by sunlight, whereas the decomposition occurs all year long, even though its impact is hidden by the powerful photosynthesis activity.
Clyde, the oxygen balance did give a definitive answer to all your questions:
Besides the 13C/12C ratio changes, O2 changes are stoichiometric coupled with organic CO2 intake and release (including burning). That includes O2 from bio-life in the oceans. O2 changes from less solubility in warming ocean surfaces is also known and of minor importance.
The diurnal changes are huge: over a year, some 120 PgC as CO2 is absorbed into the biosphere by photosynthesis during the day. At night already half of that (60 PgC) is respired by plant and soil (bacterial) respiration. The other half remains longer: between half a year (up to fall/winter) and many years, but in average again some 60 PgC/year is released by fungi, bacteria or is digested by other living creatures.
That is the main cycle, when ins and outs are in equilibrium, a huge cycle that is largely independent of the amount/press of CO2 in the atmosphere.
Note that the uptake is leading and the release never can exceed the uptake over long periods, except at the cost of total living plant mass.
The influence of the CO2 amount/press in the atmosphere is very modest: only about 2.5 PgC/year currently is absorbed extra each year by the total biosphere: one quarter of human emissions (as total mass, not only from the original fossil CO2!). That is the observed unbalance, as deduced from the O2 balance, after taking into account the O2 use from burning fossil fuels… The earth is greening…
For the oceans, one has DIC (inorganic carbon species) measurements for the surface and estimates (and closing of the carbon mass balance) for the deep oceans. That again is about one quarter of the fossil CO2 release. Remaining about half of fossil emissions (temporarily) in the atmosphere (again counted as mass).
More about the O2 measurements and partitioning of the net CO2 uptake can be found at Bender et al, especially Figure 7 at the last page:
https://tildesites.bowdoin.edu/~mbattle/papers_posters_and_talks/BenderGBC2005.pdf
Here the graph of the distribution, based on the carbon and O2 balances for the period 1990-2000. I have seen a more recent update, but have no reference:
Any and all organic material, whether it has been sequestered for a few hundred years or not, will oxidize, reducing free oxygen and produce water and carbon dioxide. Unless one can account for all the the ‘new’ H20 and CO2, AND determine its source, oxygen decline isn’t too useful in demonstrating that fossil fuels are responsible for anthropogenic CO2.
It’s the typical climate science approach. Ignore variance even though that is a direct metric for the uncertainty associated with the subject under scrutiny. Determine some average over a long period of time and assume that the average arrived out will give all the necessary answers with 100% accuracy.
Just less than 50% of the rising phase came from MME, and only 39.1% of the net is from MME.
Clearly the main contributor to the rising phase of ML CO2 is the warming ocean, with r≥.8.
Bob, the δ13C change over the seasons tells a different story…
When temperatures go up in spring, deciduous forests start to get enormous quantities of CO2 out of the atmosphere at the same time that the warming oceans expel a lot of CO2, Based on the inverse CO2/δ13C changes, the biosphere wins the contest (with a global average of about -5 ppmv/°C), thus inverse with the temperature change:
Even over year-by-year periods, the biosphere is reacting faster on temperature changes than the oceans, but this time parallel (!) with temperature changes (+3.5 ppmv/°C):
And please use variables of the same order: in the third graph, you compare temperature changes with dCO2/dt changes… If one compares the derivatives of both, dT/dt has zero trend, thus is not the cause of the trend in dCO2/dt:
dT/dt and dCO2/dt are 12 month running averages, dT/dt is enhanced with a factor 3.5 to match the amplitude of the variability in dCO2/dt. Fossil emissions are yearly
As one can see: temperature is responsible for all variability in natural sink (not source!) capacity, while human emissions are responsible for the full trends.
“As one can see: temperature is responsible for all variability in natural sink (not source!) capacity, while human emissions are responsible for the full trends.”
Clearly, as my charts indicate, the trend in CO2 is caused by large-scale flows of both MME and ocean warming, according to mass balance math.
The equatorial ocean heat content anomaly is responsible for 67% of the ML CO2 anomaly variance, including sourcing. You are 100% wrong.
“while human emissions are responsible for the full trends”
The CO2 trend is largely driven by the trend in ocean warming of SST T≥25.6°C, which I modeled in 2020, which has also increased in ocean area since 1850 as well as gotten warmer, while conforming to Henry’s Law of Solubility of Gases for CO2.
Bob, again, you are comparing apple sales with the derivative of pears sales.
In all graphs, you compare the change in temperature with the rate of change of CO2. That are variables of different order…
The variance in the derivatives is fully caused by the temperature variance, but as the derivative of the human emissions has a trend, twice the trend of the derivative of CO2 in the atmosphere and the derivative of temperature has no trend at all, the trend in dCO2/dt is fully caused by human emissions.
The problem is that you are misled by the form: any sinusoidal form is practically the same for the variable and the derivative of the variable. The only difference is that a variable may have a linear trend, but the derivative has none and there is a backward shift of pi/2 of the variability.
Here the plot of de derivatives of CO2 in the atmosphere and temperature and the temperature itself:
WfT has not the fossil emissions in its database, thus not plotted here, but the trend is about twice the trend of dCO2/dt in the above plot.
What you can see is that dT/dt and T(anom) have similar variability, but dT/dt has zero trend and dCO2/dt lags dT/dt, but T(anom) and dCO2/dt are fully synchronized. Thus which leads the other?
The first graphic at the top of your comment is one of the more compelling arguments I have seen that demonstrates that the biosphere dominates the short-term, seasonal changes in atmospheric CO2. The δ13C ratio declines during the CO2 ramp-up phase, reaches a peak at the end of Summer, and then ends up pretty much where it started out 12-months earlier. The small difference is undecipherable without error bars on the data. Having said that, I’ll venture to guess that it is the 4% of total CO2 flux that humans are responsible for.
Clyde,
Both 13C and 12C are stable isotopes and therefore both must separately satisfy mass balance principles. The mass balance equations for 13CO2 lead to a very useful plot known as the Keeling plot, where atmospheric δ13C (in CO2) is plotted against the reciprocal of atmospheric CO2.
First, here is a fairly good reference (pdf) on Keeling plots, including the basis as set out in the relevant mass balance equations: Kőhler et al (2006). The basic concept is that a linear relationship between 1/CO2 and δ13C indicates a constant value for the δ13C of the incremental CO2 and this value is given by the intercept of the plot. Figure 1 in the Kőhler paper shows the data for the Law Dome ice core going back to 1750 and provides an intercept δ13C of -13.1‰ with an R squared of 0.96.
The following two Keeling plots are based on direct atmospheric observations at Mauna Loa downloaded from the Scripps CO2 program keeping in mind that, given a linear relationship, the intercept of the linear fit is indicative of the average net δ13C of the incremental atmospheric CO2.
This plot shows both the seasonal cycle and long term trend. We are clearly dealing with (at least) two distinct trends. As such, we should not attempt to fit a linear relationship to the underlying data points. We can, however, highlight the approximate value of the two major trends. The red and green lines drawn over the data are not curve fits, but they are indicative of the true value, which shows that the annual cycle reflects a δ13C of about -26‰, consistent with it primarily reflecting the terrestrial biosphere, whereas the longer term trend reflects a δ13C of incremental atmospheric CO2 of about -13‰, much higher than variations in the biosphere or for fossil fuels (circa -28‰ according to NOAA).
The second plot is with the seasonal cycle removed (removed by Scripps). This provides a strong linear relationship reflecting the long term growth in atmospheric CO2 with an intercept of -13.4‰ and an R squared of 0.98.
According to my analyses, the equivalent values for two other observatories are:
Point Barrow: -13.2‰ and an R squared of 0.96.
South Pole: -13.0‰ and an R squared of 0.99.
See also my response to Ferdinand about the Law Dome data at the bottom of this page (currently in prep-hopefully ready later today April 13th)
Ferdinand, annual MME are just part of the annual rising phase, not enough to make up the total. If you’re going to invoke biological decomposition of land biota to fill in the entire gap every year, you’re also going to have to explain how does that sole mechanism drive the annual CO2 rising phase while it keeps time with the ocean, correlating at r≥.8, 0 lag?
Your explanation leaves out the predictable ENSO influence on CO2. How is it that more/less CO2 is emitted naturally after an El Niño/La Niña? Wouldn’t your explanation imply more/less plants die off, or did ocean outgassing have more to do with it as my plots infer?
Bob, human emissions are one-way additions, the rest are cycles. The height of such a cycle is not important, what is important is the difference between inputs and outputs of the cycle: that is what changes the CO2 level in the atmosphere.
Human emissions are one way directly into the atmosphere. As we measure only half the increase in the atmosphere of the human addition (as mass), nature only can be a net sink for the other half, not a net source. No matter that the variability matches the variability of the increase in the atmosphere… That variability is in the net sink capacity, not in a net source capacity.
Human emissions over the past 67 years were over 200 ppmv, more than large enough to be the cause of the 100 ppmv increase in the atmosphere.
The influence of SST over the same period was less than 10 ppmv, using the formula of Takahashi:
(pCO2)seawater at Tnew = (pCO2)seawater at Told x EXP[0.0423 x (Tnew – Told)]
That gives:
It is not that simple seems to be generally applicable. Where CO2 came from seemed simple.
One thing I discovered from recording co2 levels with datalogging equipment is that photosynthesis by the coastal vegetation at my location, 19 degrees south, west coast of the Coral Sea, starts at sunrise and always stops at midday. The vegetation has enough to start producing lignin. Our hardwood trees can be 10m tall in about 3 years. There are other bursts of co2 later in the day, which I put down to decay of vegetation in the shoreline. Occasionally bushfires along the shore, on Magnetic Island will register, and from inland if the wind is from that direction. The predominant air flows are from the north-east. There ain’t no coal fired power stations out there.
The hydrosphere is net sink.
The biosphere is a net sink.
The human tapped carbon reservoirs are a net source.
Because human tapped carbon reservoirs are a net source and because the biosphere and hydrosphere are net sinks then humans are the cause of the net gain of carbon in the atmosphere. The law of conservation of mass is unequivocal and indisputable on this matter.
Since it isn’t the ‘control knob’ of the the Earth’s climate, I don’t give a fig where it comes from.
nailed it!
Speaking of figs- my several potted figs are growing faster than ever. Partly because I’ve fertilized them more than before- but also I sense they love the extra CO2. I put them out in the garden in the summer but leave them in the house the rest of the year. One of my grandfathers brought the original from “the boot” when he came here around 1910. Every year I harvest maybe 3-4 dozen figs. They are extremely delicious when picked right of the tree.
Wrong science of skeptics reflects badly on items where skeptics are right…
That is true of every debate and applies to those on both sides of the debate.
I couldn’t agree more.
For those not aware, Belgian nonagenarian Ferdinand Engelbeen https://co2coalition.org/teammember/ferdinand-engelbeen/ is an éminence grige of climate realism. Not some Mann of Science. His work is meticulous and extremely impressive.
He corrected me (very gently I may add) in my misguided view that the CO2 rise in the atmosphere might not be primarily due to fossil fuel burning and cement manufacture. The depth of his knowledge on this subject is without peer in my view.
Dankuwel voor uw deelname aan deze discussie!
(Thank you for taking part in this discussion!)
Wow, thanks a lot Rich Davis for your kind words… Hartelijk dank… A little overblown: got 81 years of age by now, but you never know that we can reach the 90’s hopefully in good health…
I am thinking that such discussions come and wane with some solar cycle. Most “new” arguments are just repeating the arguments of 22 years ago in the period 2000-2005. Maybe the 22-year full solar magnetic cycle?
Will -again- take some time and patience…
Let’s not call it my error, but my prophecy! 😛
It is one more chink in the CAGW hypothesis along with others like UHI and clouds. When will it fall into a clump of nothing.
Your logic is flawed. The ratio of your alleged net source versus net sink is missing.
The hydrosphere is a net sink at times and a net source at times.
The biosphere is a net sink at times and a net source at times.
You omit other sources.
I suppose you will give up carbonated drinks to do your part in the climate crusade.
And the biosphere is less of a sink the more vast areas are covered with wind and solar “farms”- and urban sprawl too.
Scientists do expect the biosphere to flip from a net sink to a net source in the future, but we’re not there yet.
Whenever I see any claim that starts with “scientists say . . . “, I grab my wallet and hold it firmly closed.
scientists say blah, blah, blah COULD happen! And everyone freaks out.
I do the Space Balls crew reaction.
Reminds me of “journalists” – “Experts say” -which to me means watch your step, you don’t want bull crap on your shoes.
That is almost as bad as “anonymous sources, who don’t have permission to talk about the subject, claim …” Totally unverifiable and the only reason for saying it is if the journalist making the claim has his/her/its feet held to the fire, they can disclaim any responsibility because it was an anonymous source. Heads they win, tails we lose. No reputable journalist should EVER use that line. Instead, they should say, “No one we talked with was willing to go on record; however, it is our opinion that …” It may be an act of cowardice, but I suspect it is just a cover for unsupported propaganda that people who want it to be true will accept uncritically.
They expect that to happen based on what logic? Maybe if some governments keep pushing for net zero and we cover millions of acres with wind and solar farms, that would get close. What other reasons? Trees are now growing faster due to increase CO2.
Which scientists? What data? When? How much?
And where is the social justice appendage of “our most vulnerable…”
But those effects are anthropogenic.
Exactly. Those are examples of a direct causal link. Indirect casual links also exist though. For example if humans do something that increases the SST by 1 C then the 16 ppm equivalent outgassing by the ocean would then be categorized as anthropogenic as well because we appear in the causal chain.
Just curious, what exactly could humans do to raise SST by 1 C, and how long would it take?
Well, the maximum time it could possibly be (given the inability to separate natural from anthropogenic causes) is the 0.13 C/decade over the oceans (in the lower troposphere) as revealed by Dr. Roy Spencer in his March 2025 UAH 6.1 satellite-derived record spanning a period about 45 years. So it would take continued warming at that rate (a heroic assumption in itself) a little less than 100 years to reach the 1 C increase you identified. [Really scary, huh?]
Yeah, yeah, I know UAH 6.1 is calculating the temperature of the air above the oceans. However, since the oceans warm the atmosphere, the trend of 0.13 C/decade should track the temperature trend of the surface waters (even if some adjustments need be made). Can anybody outside of CliSciFi give me a better estimate?
Anything that causes the planetary energy imbalance to become positive. This includes increasing GHGs emissions, decreasing aerosol emissions, decrease albedo via land use changes, etc. It took about 50 years for the most recent 1 C rise to occur which, according to the consilience of evidence, is primarily the result of anthropogenic factors.
Consilience! Well wouldn’t you know, a new reason to reject scientific measurements along with their uncertainty for determining truth.
Here is a discussion of “consilience”.
https://issues.org/jamies/#:~:text=One%20of%20his%20examples%20of,the%20prior%20induction%20is%20based.
You should notice the word “induction”.
Here is a reference that discusses deductive and inductive logic.
https://plato.stanford.edu/entries/logic-inductive/
In essence, consilience implies that there is only correlation which may or may not lead to a true conclusion. It does not guarantee causation without scientific evidence based on measurements and associated mathematics.
The ‘evidence’ is frequently cherry-picked, meaning it is presented when it supports the meme, but generally ignored when it raises embarrassing questions.
The “say what you need to say at the time” argumentative strategy.
The law of conservation of mass is not flawed.
The sources and sinks are not missing.
[Friedlingstein et al. 2025]
That is patently false.
What sources have been omitted?
Vulcanic f.e., Black Smokers at seagroud, earth quakes or other tectonic movements to name only some…
Volcanic is less than 1% of human emissions, based on years of monitoring the Mount Etna, one of the 5 most active subduction volcanoes of the world.
Undersea volcanoes emit CO2 that readily dissolves in the extreme pressures of undersaturated (for CO2) deep ocean waters, with a few exceptions, like the late Hunga Tonga eruption.
https://www.cambridge.org/core/books/deep-carbon/carbon-dioxide-emissions-from-subaerial-volcanic-regions/F8B4EFAE0DAF5306A8D397C23BF3F0D7
worth reading!
Yes important on geological times (200,000 years!) not on 170 years scale…
Again, an assertion without a supporting citation. Because volcanic events are episodic, your statement might be true in some centuries, and not in others. The problem is we don’t really know because we haven’t even mapped all the submarine volcanoes (100,000 and counting) and active vents, let alone measured the emissions. And while Mt. Etna might be a reasonable proxy for active terrestrial volcanoes, there are others like https://www.kabiraugandasafaris.com/ngorongoro-crater.html that appear to exude much more CO2 than Etna. Also, there are other places like Long Valley Caldera (Calif.), that emits copious amounts of CO2, which was only discovered in recent decades:
https://www.usgs.gov/publications/invisible-co2-gas-killing-trees-mammoth-mountain-california . The sampling of terrestrial volcanoes is of questionable veracity.
What evidence do you have to support that assertion?
https://scitechdaily.com/nasas-satellite-just-uncovered-100000-hidden-mountains-beneath-the-ocean/
Clyde,
The deep ocean waters are undersaturated in CO2, due to their low temperatures. At the main sink place for the surface waters into the deep oceans, the N.E. Atlantic, the cold waters have a pCO2 of only 150 μatm, way below the atmosphere at 425 μatm (~ppmv). Under 100 or more bar water pressure at the top of the volcanoes, how much CO2 will escape to the atmosphere do you think?
And when dissolved in the total mass of the oceans, how much influence has that on DIC levels in the deep oceans?
It happens very seldom that undersea volcanic eruption gases reach the atmosphere. Only with near-surface or huge explosions like the recent Hunga Tonga eruption…
Those are really non sequiturs because that water is remote from the atmosphere. However, the CO2 doesn’t disappear. Therefore, if the water up-wells, (as it does in the Tropics and along continental shelves) experiencing less pressure and increased temperature, the CO2 is still available to out-gas. The issue about the larger number of potential submarine volcanic sources is that the CO2 concentration will not be uniform in concentration or over time. Thus, deep episodic releases might well be missed but will still add to the atmospheric abundance. That is, the estimates of submarine volcanic emissions are almost certainly a lower-bound because of their ubiquity, but episodic behavior makes it almost impossible to measure. What will happen to the carbon in the pelagic muds if they are baked by an eruption? The organic delta-13C ratio will be mixed with the volcanic delta-13C, confounding the attempt to distinguish the source.
Scientists like Friedlingstein et al. are fully aware of the geological sources of carbon. That’s how you and I know about them. Scientists told us.
So your interpretation was wrong
My interpretation of the law of conservation of mass is that the change in mass of a reservoir is given by the mass that goes in minus the mass that comes out. Mathematically this is ΔM = Min – Mout.
Applying the LoCM to all reservoirs in a system tells us that if ΔMi > 0 for {i: 1 to n-1} then it must be the case that ΔMn > 0. In plain language this means reservoir n must be the source of mass for reservoirs 1 to n-1 and whatever agent caused the loss of mass from n is necessarily the cause of the mass gain in reservoirs 1 to n-1.
That is a mathematical fact; not an interpretation.
Typo. That should be ΔMn < 0 to match the plain language description that follows.
No. It applies to individual chemical reactions, not reservoirs.
https://www.nature.com/scitable/knowledge/library/the-conservation-of-mass-17395478/
You don’t think the law of conservation of mass (LoCM) applies to the land, ocean, biosphere, atmosphere, etc. reservoirs?
Do you even accept the LoCM at all? And if so under what seemingly narrow conditions do you constrain it to?
Carbon is not the issue.
Harmless CO2 is not a problem.
Carbon is THE focus of the carbon cycle. That’s why it is called the carbon cycle.
Whether it is a problem or not is a matter of debate.
As long as you continue to use alarmist vocabulary, you will continue to lack any credibility.
I don’t personally feel like the “carbon cycle” is an alarmist term. If “carbon cycle” is alarming or offense to you then perhaps we can agree on another reasonably term for the same concept that you find less alarming and/or offense. If it is the concept that you find alarming and/or offense then my friendly advice is to take a step back from this article and perhaps engage with articles that you find less alarming and/or offense.
Increased agriculture, deforestation, ….
Yes Tim, broadscale deforestation and urbanisation all around the world form the “double-bunger” effect that accounts for the incremental increases in temperature stations.
Start with Henry’s Law and go forward.
Plants die and decompose. Look at the MLO data annual cycle.
Net result of Henry’s law: 13 ppmv CO2 increase in the atmosphere at equilibrium with the warming of the ocean surface (0.8°C for the highest temperature increase in the reconstructions)…
The annual cycle certainly is caused by the biosphere, but inverse with temperature: higher temperatures = lower CO2 (~5 ppmv/°C).
On year by year scale again plants are the dominant factor, but here higher temperatures = higher CO2 and reverse (Pinatubo, El Niño, ~3.5 ppmv/°C)
On longer term: decades to multi-millennia, the oceans are dominant with ~16 ppmv/°C over very long term.
The point of the post was showing “the scientists say” CO2 is resident in the atmosphere for hundreds of years if not thousands, which we know is false.
If there are annual cycles in the MLO data, then CO2 is not a long term resident.
Scientists don’t say CO2 is resident for hundreds or thousands of years. They say it is about 5 years.
What scientists do say is that the mass adjustment for a pulse of CO2 is on the order of hundreds of years.
These are two different concepts. Do not conflate them.
If you need Ferdinand, myself, etc. to explain the difference let the community know and I’m sure someone will help you out.
Is that what the pulse of 14C shows?
Clyde, the 14C pulse fades at a speed of around 20 years e-fold decay, already way higher than the residence time of 4 years, thus falsifying the residence time as irrelevant to remove an excess amount of CO2.
Then why is it only 20 years while it is around 50 years for a bulk excess 12/13CO2 in the atmosphere?
That has two causes:
No. The pulse of 14C (assuming you are talking about the bomb spike) shows the residence time. Well…sort of…it’s complicated by the fact that the bomb spike wasn’t an instantaneous spike. My problematic is that the decay curve also isn’t the result of bomb testing alone anyway. It includes the other sources of 14C production over the decades. My point is that residence time estimates from a trivial analysis of the bomb spike decay curve will be skewed too high.
This seems too slick to be acceptable at face value. The warming is only happening above the thermocline, which varies in depth. The warming also varies laterally with currents such as the Gulf Stream, and with the state of the AMOC. The out-gassing is a function of both the temperature increase, the volume of water warmed, the latitude, the concentration of dissolved CO2, and the partial pressure of atmospheric CO2.
Clyde,
Be happy that it is only the ocean mixed layer temperature that is involved. If it were the deep oceans, we would be at around 150 ppmv in the atmosphere, good to kill 93% of all plant life (and the rest of us),
There is a dynamic equilibrium between the ocean surface and the atmosphere: a lot of CO2 is released near the equator and other warm oceans and a lot is absorbed in colder waters, sinks near the poles to return near the equator.
The uptake / release is a matter of pCO2 difference between ocean surface and atmosphere with the formula:
F = k*s*ΔpCO2
Where k = transfer coefficient (wind speed)
s = solubility parameter (composition)
Since a few decades there are plenty of ocean pCO2 measurements and these show an average ΔpCO2 of 7 μatm higher in the atmosphere than in the ocean surface. Thus the net flux is from the atmosphere into the ocean surface (and into the deep oceans via the direct sinks).
Feely et al has compiled hundred thousands of such measurements made by many surveys into one year, 1995:
https://www.pmel.noaa.gov/pubs/outstand/feel2331/exchange.shtml
and following sections.
With the maps at:
https://www.pmel.noaa.gov/pubs/outstand/feel2331/maps.shtml and next section:
“This map yields an annual oceanic uptake flux for CO2 of 2.2 ± 0.4 Pg C/yr”.
But the data processing used to analyze the measurements often is. That is, the assumptions used to assemble an equation to be balanced may not be justified. That is what I still have to articulate in the future.
That is certainly a much better argument than ignoring the LoCM. However, the problem I’ve seen is that people who challenge the best estimate of mass changes in GtC often do so while either ignoring the LoCM or just outright violating it. It is important that all criticisms of the data be consistent with the LoCM or curmudgeonly skeptics like me will take issue with the criticism right off the bat.
It’s exactly what Freeman Dyson always criticized climate science for – a lack of holistic analysis. Just assume everything is constant except factor you are looking at. It makes things simpler – but also many times it winds up wrong.
Another flaw: Net gain of carbon in the atmosphere is due to burning biomass. Particulate carbon comes from fires.
Try reading and comprehending the paper.
Sources missing. Yes, I’m going to work that pun for all it’s worth.
Humor – a difficult concept.
— Lt. Saavik
If all of the 285 GtC gain in the atmosphere came from the biosphere then biosphere would have a 285 GtC loss. That’s the law of conservation of mass. Instead the biosphere gained 220 GtC. Your argument is a violation of the law of conservation of mass..
[Friedlingstein et al. 2025]
Like all of climate science the measurement uncertainty if the figures you give are 1. missing and 2. Likely greater than the differences you are attempting to identify.
What *is* the measurement uncertainty of your figures? Do you have the faintest idea?
“Measurements?”
We doan need no stinkin’ measurements.
Emissions of fossil fuels are quite accurate, based on sales (taxes!) and burning efficiency. Probably underestimated, certainly not overestimated.
CO2 levels in the atmosphere are very accurately measured at a lot of stations all over the globe.
That makes that the difference: increase in the atmosphere minus human emissions is quite accurately known. Thus the difference between all natural ins and outs is quite accurately known: more sink than source in the past 67 years.
Other fluxes are based on pCO2, O2, δ13C, DIC,… measurements with larger margins of errors but still accurate enough to have an idea where the excess CO2 from humans (as mass, but also the change in 13C and 14C) goes…
For the biosphere the O2 changes are the leading measurement and the chlorophyll measurements: the earth is greening:
http://www.bowdoin.edu/~mbattle/papers_posters_and_talks/BenderGBC2005.pdf
In order to assign accurate attribution percents one needs accurate measurements of ALL the parts. Do we accurately know how much CO2 termites generate? How about accurate measurements of how much the oceans contribute, as this article discusses? How about weathering?
IOW, how much gets attributed th FF only, rather than an accurate accounting of all sources.
Jim, please… It is only of academic interest to know any individual CO2 flux to any accuracy to know the cause of the CO2 increase in the atmosphere.
We know the fossil fuel emissions with quite high accuracy.
We know the increase in the atmosphere with high accuracy
Thus we know the difference between these two with quite high accuracy.
Increase in the atmosphere = human emissions + natural emissions – natural sinks.
For 2020 roughly:
5 PgC = 10 PgC + X – Y
X – Y = -5 PgC
With 890 PgC in the atmosphere one can calculate the residence time:
RT = 890 / Y
If X = 20 PgC, Y = 25 PgC, RT = 35.6 years
If X = 210 PgC, Y = 215 PgC, RT = 4.1 years (figures IPCC)
If X = 2000 PgC, Y = 2005 PgC, RT = 0.44 years
As a matter of fact: as long as human emissions are larger that the increase in the atmosphere, it doesn’t matter at all how much natural CO2 circulates through the atmosphere nor the resulting length of the RT. Even if some individual natural flux doubled or halved from one year to the next year, that is not of the slightest interest for the cause of the increase…
“im, please… It is only of academic interest to know any individual CO2 flux to any accuracy to know the cause of the CO2 increase in the atmosphere.”
In other words, don’t confuse me with the facts!
“We know the fossil fuel emissions with quite high accuracy.”
No, you don’t. If you did you could actually quote what the accuracy is.
“We know the increase in the atmosphere with high accuracy”
No, you don’t. If you did climate science wouldn’t have to make the simplifying assumption of “all CO2 is well mixed” when that is obviously wrong.
“Thus we know the difference between these two with quite high accuracy.”
Measurement uncertainty GROWS with every uncertain component added into the mix. All you’ve done here is magic thinking and hand waving. Assuming that all of the data is 100% accurate is *not* what physical scientists should be doing if they expect to be taken seriously.
Tim, we know fossil fuel sales quite exact thanks to sales (taxes) and we know the burning efficiency of each type of fuel:
5 +/- 0.5 ppmv/year
In my opinion underestimated, due to the human nature to avoid taxes and some countries (like China) to reduce their official “burden”.
If underestimated, that only adds to the real human input.
Not included 1-2 PgC/year of land use changes, which also adds to the human input.
CO2 levels in the atmosphere are very accurately measured within +/- 0.2 ppmv in 95% of the atmosphere that is well mixed. Not in the first few hundred meters over land where there are huge sources and sinks at work (but even there a lot of stations are at work to follow plant uptake/release).
The difference between all stations from near the North Pole to the South Pole for yearly values is not more than 5 ppmv while some 100 ppmv is exchanged per season between oceans, atmosphere and biosphere.
I call that extremely well mixed for a natural item…
Even the 5 ppmv difference between the NH and the SH is caused by human emissions: 90% are in the NH and the ITCZ allows only an exchange of about 10%/year in air masses between NH and SH.
That is about the measurements within one year. Thus with a maximum error of 0.7 ppmv per year for both measurements combined (but in fact lower).
The measured increase currently is 2.5 ppmv/year and the natural variability for the extremes (Pinatubo, El Niño) is +/- 1.5 ppmv in one year. That means that the error + natural variability margin for one year still is smaller than the human signal. Even if we don’t know one natural flux in or out.
Any small measurement error in one year is compensated by a new measurement in the next year. The total increase since 1958 is already over 100 ppmv CO2, while human emissions over the same time frame are over 200 ppmv CO2. Nature was a net sink of over 100 ppmv CO2. There is simply no room for new theories that nature is the cause of the increase…
“Tim, we know fossil fuel sales quite exact thanks to sales (taxes) and we know the burning efficiency of each type of fuel:”
It’s been pointed out to you at least twice that knowing the sales does *NOT* accurately tell you the CO2 contribution anywhere from the use of that fuel. One example is the change in CO2 production from autos due to the time-based degradation of catalytic converters over time. Another is the contribution globally from termites, etc over time since it is not a factor that is measured globally with any accuracy at all.
Saying that the law of conservation of mass applies is just a dodge for avoiding actually addressing the measurement uncertainties that apply throughout the biosphere.
“CO2 levels in the atmosphere are very accurately measured within +/- 0.2 ppmv in 95% of the atmosphere that is well mixed.”
But that is where the SMALLEST proportion of CO2 exists! Trying to use that to estimate the total is bound to have significant measurement uncertainty.
“The difference between all stations from near the North Pole to the South Pole for yearly values is not more than 5 ppmv while some 100 ppmv is exchanged “
Again that is a 5% difference. If you don’t consider that to be significant enough to be a huge source of uncertainty then you are just totally ignoring metrology protocols.
“That means that the error + natural variability margin for one year still is smaller than the human signal.”
You apparently can’t see the forest for the trees. You are trying to use measurements from one location where, supposedly, the CO2 is well-mixed to characterize the total, including where the largest proportion of CO2 exists.
“The measured increase currently is 2.5 ppmv/year and the natural variability for the extremes (Pinatubo, El Niño) is +/- 1.5 ppmv in one year. That means that the error + natural variability margin”
Neither of the values you give have an associated measurement uncertainty interval. How do you know if they are less than the human signal? Once again you are apparently using the common climate change meme that “all measurement uncertainty is random, Gaussian, and cancels”.
A .7 error (is that +/- or just +?) compared to a total of 4 is a 17% uncertainty. That is HUGE! And you just seem to blow it off.
“Any small measurement error in one year is compensated by a new measurement in the next year.”
Once again, this is the common climate science meme that “all measurement uncertainty is random, Gaussian, and cancels”. It’s a garbage assumption guaranteed to give garbage results. Measurement uncertainties ADD, they ALWAYS add. Each data point is a measurement of a different measurand. When you have different measurands combined into a data set their measurement uncertainties ADD. If your measurement uncertainty is 0.7 for each then your total measurement uncertainty for the two measurements will be 1.2 at a minimum and 1.4 at a maximum.
You should have learned how to handle measurement uncertainty in any physical science labs you had at university. If they didn’t teach you this then your education was sadly lacking in scientific discipline.
No, it is not “only of academic interest”. That is attempting to justify hand waving as accurate and precise.
When dealing with small percentages, accuracy is very important. If you wish to show your numbers are sufficient, here are two categories you should be able to quantify along with references.
There are many others that should be quantified also.
Don’t try to justify “back of the envelope” calculations as having any scientific rigor. That just doesn’t occure.
Back when I had my remote sensing business, I had a project using Landsat satellite imagery in Africa. I examined the available preview imagery from the EROS Data Center before placing my order for the digital data. What I wasn’t able to see in the reduced spatial-resolution preview imagery was just how thick the smoke was south of the Sahara. It severely impacted the usability of the imagery. I wouldn’t be surprised to discover that the CO2 was also elevated.
Jim, the carbon mass balance remains exactly the same if you subtract two quite accurately known variables than by using the hundreds of ins and outs that make up one of these variables…
“if you subtract two quite accurately known variables”
Except you *don’t* know the variables accurately as has been demonstrated quite well in this discussion. You want us to believe that your numbers are 100% accurate. They aren’t. No measurements are. And your figures aren’t even measurements – they are guesses.
It also matters *HOW* that carbon mass balance is obtained. Without that you can’t judge the impact of the factors involved in reaching that mass balance. It isn’t the mass balance that causes the biosphere impacts, it is how the mass balance is obtained.
And you have yet to actually quote any measurement uncertainty interval for *anything*. You haven’t even given us a measurement value +/- measurement uncertainty for what the total mass is!
We do not “know” the CO2 emissions from hydrocarbons and coal.
We estimate the consumption. We apply generalized averages what burning each fuel produces. The key is that we estimate consumption based on sales and taxes. How accurate are the bills of ladening in shipping? 100.2 tons versus 100 tons?
We know the accuracy at specific heights and locations. We also know there is a variation between urban and rural. We also know their are variances between the northern hemisphere and the southern hemisphere.
This does not support the assertion that we know with high accuracy.
Hardly matters…
What was sold, sooner or later will be burned. What is not burned in one year is added next year to the smokestack.
The same for the levels and errors in measurements: what is over or underestimated in one year will be measured next year.
Well mixed doesn’t imply that CO2 is exactly the same at every place on earth at the same second in time. But if one finds only 5 ppmv difference in yearly CO2 level from near the North Pole to the South Pole, while some 100 ppmv CO2 is exchanged each year, I call that well mixed…
“The same for the levels and errors in measurements: what is over or underestimated in one year will be measured next year.”
Measurements don’t work that way. Measurement uncertainties *ADD*. Each data point has measurement uncertainty and they *add*, either directly or in quadrature.
This is nothing more than the common meme in climate science of: “all measurement uncertainty is random, Gaussian, and cancels”. Without ever actually justifying either assumption – random and Gaussian.
“But if one finds only 5 ppmv difference in yearly CO2 level from near the North Pole to the South Pole, while some 100 ppmv CO2 is exchanged each year, I call that well mixed…”
5/100 is a 5%. That is a SIGNIFICANT variance. That is *NOT* well-mixed.
Tim, the 5 ppmv is on a 425 ppmv level, that is just over 1% and even that is man-made, not a problem of the measurement method. That is the result of human emissions that are for 90% in the NH.
The 100 ppmv is from the 25% that is going in and out the atmosphere within that year. The only point of interest is that the 100 ppmv in and out causes so little disturbance in the atmosphere….
“Tim, the 5 ppmv is on a 425 ppmv leve”
FE: “But if one finds only 5 ppmv difference in yearly CO2 level from near the North Pole to the South Pole, while some 100 ppmv CO2 is exchanged each year, I call that well mixed…”
You moved the goal posts. Is the 5ppmv the difference from one pole to the other or is it the measurement uncertainty of the actual measurement?
Are you saying the are both the same?
That isn’t true. We know the individual measurements from stations like MLO with high precision. However, when the wind it blowing the wrong direction, the measurements are (subjectively) discarded because they are assumed to be contaminated with volcanic emissions. Therefore, to integrate the area under the curve, we have to interpolate. Probably acceptable, but it does introduce some uncertainty. Where things get more dicey is that despite CO2 being characterized as “well mixed,” various NASA reconstructions from OCO-2 show diurnal ‘flickering’ and wispy streaks of CO2 at different altitudes. What is even more damning is the significant increase in the seasonal range of CO2 as one moves from the South Pole to the North Pole. There are sufficient sampling stations to give us the general behavior of CO2, but because integrating all the interpolated values introduces uncertainty, the final estimate of total CO2 in the atmosphere is no where near as accurate as for individual monitoring stations. It is wishful thinking that cannot be defended.
Clyde, there is no significant difference in yearly average between retaining all raw data at Mauna Loa and using only the “reliable” data. If you are interested in the CO2 emissions of the volcano, then measure near the volcanic vents. For global CO2 data, these are of no interest, only disturbances and not used (but still available!).
Here the full set of raw data for 2008 plotted with the “cleaned” daily and monthly data for Mauna Loa and the South Pole:
Mauna Loa has more outliers to lower values than to higher values: in the afternoon, upwind conditions may bring slightly CO2 depleted air from vegetation in the valleys up to the station.
For the South Pole, far less outliers, but more mechanical problems for the harsh conditions there…
Seasonal changes (mainly caused by vegetation) are of zero interest, as we are only interested in the year by year increase.
An average difference of some 4 ppmv over a full year between MLO and SPO on a level of near 400 ppmv (1%) with 25% exchange of CO2 over the seasons per year at a distance of 12,000 km. Who said “not well mixed”?
You show me the picture of some ‘fuzzy’ purple and green abyssal creature and claim “We know the increase in the atmosphere with high accuracy.” The standard deviation for the daily CO2 concentration is composed of both seasonal variations and daily variations that are probably largely random. I do not share your definition of “high accuracy.” “Selected” data is another word for “subjective.”
I’m certain that nobody has done a rigorous sampling/measurement program for the oceans. Inasmuch as there is the generally unstated assumption that the world was somehow in equilibrium before the Industrial Revolution, there was probably at least a subconscious bias to make the mass-balance equations balance for the in-out fluxes from the ocean. Thus, the alarmist advocates find them in the classic situation of subtracting a small number from a really big number and claiming that the difference is well-characterized.
Out of curiosity, do these estimates of CO2 emissions include coal mine fires?
Or even 6000 year coal seam fires:
These are included in the total sources of natural CO2 and thus in the net sink rate of CO2 in both the oceans and vegetation. We don’t know the total natural sources, but we know the net sink rate in nature, because that is equal to the difference between increase in the atmosphere and human emissions…
How much due to human respiration and how accurately is that measured?
Is included in the oxygen balance which shows that the biosphere as a whole is a net sink for CO2 at about 1.25 ppmv/year nowadays.
In general, people can’t eat more than was produced before by photosynthesis…
http://wattsupwiththat.com/2015/05/05/anthropogenic-global-warming-and-its-causes/
“Emissions of fossil fuels are quite accurate, based on sales (taxes!) and burning efficiency. Probably underestimated, certainly not overestimated.”
A typical climate scientist answer. Sales taxes tell you only how much is sold. It does *not* tell you the emissions from that product. The actual emission level from that amount of fuel is a highly complex mix of efficiency of different burning processes including catalytic converters in automobiles. Measurements of the burning products certainly has uncertainty which is never stated. It is just assumed that the wags are 100% accurate.
“CO2 levels in the atmosphere are very accurately measured at a lot of stations all over the globe.”
So what? As with temperatures any “average” calculated from those measurements accumulate measurement uncertainty with the addition of every data point. Yet climate science, once again, assumes that their “average” is 100% accurate with no measurement uncertainty. Climate science just applies their idiotic memes of 1. “all measurement uncertainty is random, Gaussian, and cancels, 2. averages can increase accuracy and, 3. averaging increases resolution of measurements.
“Other fluxes are based on pCO2, O2, δ13C, DIC,… measurements with larger margins of errors but still accurate enough to have an idea where the excess CO2 from humans (as mass, but also the change in 13C and 14C) goes…”
Which is *NOT* an answer to the question of what the measurement uncertainty of CO2 is. “accurate enough” is not a physciial science answer, it is the refuge those that have no idea of what the actual uncertainty is because they’ve never prepared a comprehensive uncertainty budget.
This is incorrect. The uncertainties are not ±1 GtC as you claim.
The uncertainties are provided in table 8.
Tim, while the uncertainties aren’t stated explicitly, they are shown graphically as a hatched area, albeit it also isn’t stated whether it is for a 1-sigma or 2-sigma probability range. It is still germane that there is no uncertainty shown for the budget imbalance, and ALL the uncertainties appear to be larger than the ‘imbalance.’
It’s not even obvious if those areas are the “standard deviation of the sample means” or if they are actually propagated measurement uncertainties. For either it’s not enough to just show the areas on the graph. Any figures given in the text should include the measurement uncertainty in the form of “stated value +/- measurement uncertainty”. Leaving off the “measurement uncertainty” implies the stated value is 100% accurate meaning any further calculations are also 100% accurate.
Clyde, even for one year, the natural imbalance + error is smaller than the measured increase per year. Only with a few borderline (El Niño) exceptions. after a few years, the “signal” certainly passes the “noise” and after 67 years of measurements, one can be very certain that there is an over 100 ppmv CO2 increase in the atmosphere, caused by over 200 ppmv human emissions…
The uncertainty in the *increase* grows with every year you add to the sequence. Pretty soon it surpasses any possible ability to calculate an accurate value.
Do I need to go through the sequence of adding uncertainties again?
I got a down vote for something that no one had the courage to challenge.
That’s because it’s based on who you are and not on what you say.
Yes, unfortunately, that seems to happen on both sides.
I gave you an upvote to offset it. The authors state 1σ. The uncertainty on the imbalance is best seen in figure 4.
I returned the favor.
CO2 is not carbon.
CO2 is composed of carbon. It is therefore a carrier of carbon. If CO2 is in the reservoir then carbon is in the reservoir.
You continue to conflate carbon with CO2 in your postings.
Doing so destroys all credibility of whatever you post.
I’m not saying carbon is CO2. I’m saying CO2 is composed of carbon.
Are you challenging the fact that CO2 is composed of carbon?
CO2 has 2 mols of Oxygen and only 1 mol of Carbon.
Why call it “Carbon” as shorthand, rather than “Oxygen”?
(is it that “Oxygen” doesn’t convey something dirty and black like “Carbon”
and also doesn’t that imply that using “Carbon” is raaaaacist?)
I’m not calling CO2 carbon. I’m calling CO2 a carbon based molecule or a carbon carrier.
And when I talk about carbon in the atmosphere I literally mean carbon with mass units of GtC.
I do this for 2 reasons. First, it is because I’m discussing the broader carbon cycle. Second, it is because carbon exists in the air, land, and ocean in many forms.
This also helps curtail a whole branch of strawman arguments and accusations that I believe CO2 is the only way carbon can exist in nature.
Carbon must be conserved, no matter the form where it is incorporated.
Except for radiocarbon 14C (with extreme low presence), it doesn’t matter in what form carbon is transferred between the different compartments.
In the atmosphere it is CO2 (and methane) which are of importance.
In the oceans it is CO2 (1%), bicarbonates (90%) and carbonates (9%) that are part of the carbon cycle.
In the biosphere it is in thousands of different molecules: hydrocarbons (starch, sugars, cellulose) and a host of other stuff.
Because of the conservation of carbon mass, one talks about the carbon cycle, as good as one talks about the nitrogen cycle (NOx and NH4 alike), the phosphor cycle in agriculture, etc…
You mention the biosphere. How much “carbon” is sequestered in plants and animals over their lifetimes. In humans alone there must be a large amount when including the feeding of each one. Humans don’t poop CO2, so it must remain sequestered for some length of time.
CO2 is 40,000 ppmv in what you breath out,,,
That is thanks to what was sequestered before out of the atmosphere by photosynthesis… Thus you are part of the carbon (and oxygen) cycle, just like termites and other insects…
The Baltica Sea is a net source, imagine 😁
Your claims are assertions without logic or (pardon the pun) source.
My logic is the application of the law of conservation of mass.
My source of net flows is based on the abundance of academic literature including but not limited to [Friedlingstein et al. 2025].
Your sources are as mentioned not complete at all, bad for you and your unacademic literature.
That the biosphere is a net sink for CO2, not a net source is reflected in the greening of the earth, even NASA/GISS has to admit it:
https://www.nasa.gov/feature/goddard/2016/carbon-dioxide-fertilization-greening-earth
And proven by the oxygen balance:
http://www.bowdoin.edu/~mbattle/papers_posters_and_talks/BenderGBC2005.pdf
Did I contradict?
If the biosphere is a net sink – always – then why has it varied so much over the millennia?
The biosphere is a proven net sink in the past years since about 1980, when accurate O2 measurements were available (a fraction of a ppmv on 210,000 ppmv is not easy to obtain). Before 1850 and the extra CO2 in the atmosphere, the biosphere probably expanded and retreated together with changes in global temperatures. That should be reflected in the 13C/12C ratio, if the biosphere was leading. Because that was not the case for the previous 800,000 years, despite huge changes in temperature and CO2 level, the ocean surface temperature was the main cause of change in CO2 level in the atmosphere.
The biosphere oscillates between growth and decay.
What are you basing 1850 levels on? Ice cores? Sediments? Or actual measurements?
“Modern greenhouse hypothesis is based on the work of G.S. Callendar and C.D. Keeling, following S. Arrhenius, as latterly popularized by the IPCC. Review of available literature raise the question if these authors have systematically discarded a large number of valid technical papers and older atmospheric CO2 determinations because they did not fit their hypothesis? Obviously they use only a few carefully selected values from the older literature, invariably choosing results that are consistent with the hypothesis of an induced rise of CO2 in air caused by the burning of fossil fuel. Evidence for lacking evaluation of methods results from the finding that as accurate selected results show systematic errors in the order of at least 20 ppm. Most authors and sources have summarised the historical CO2 determinations by chemical methods incorrectly and promulgated the unjustifiable view that historical methods of analysis were unreliable and produced poor quality results”
https://climatecite.com/wp-content/uploads/Beck-CO2.pdf
Ice core CO2 measurements are direct measurements in ancient air. Etheridge et al (1996) performed measurements of CO2 in the firn and ice at Law Dome and found similar CO2 levels in the enclosed air bubbles of the ice as at the South Pole for the overlapping period 1958-1978 for the same gas age, with the same method (NDIR):
Ice core measurements are very accurate (1.2 ppmv – 1 sigma) for multiple samples at the same depth and between ice cores even under extremely different physical conditions (snow deposit, temperature) the difference is less than 5 ppmv for the same average gas age.
The only drawback is the resolution, which depends of the local snow accumulation, but that also defines the length of the record down to bedrock. The resolution is better than 10 years over the last 150 years up to 560 years over the past 800,000 years.
See: https://co2coalition.org/publications/measurement-of-co2-concentrations-through-time/
About the work of the late Ernst Beck: the methods used in the past were not that bad (+/- 9 ppmv), but where was measured was a mess: within forests, towns, near huge sources… Only when was measured on board of sea ships over the oceans and at the seaside with wind from the sea, in deserts or at the top of mountains, the levels were around the ice core measurements… All the other measurements were good for the data dust bin…
I have had a lot of direct discussions with him in the period 2000-2010, until his untimely death.
See my comment on Beck’s work that was later published in 2022:
https://scienceofclimatechange.org/wp-content/uploads/Engelbeen-2023-Beck-Discussion.pdf
So CO2 is not well mixed as evidenced by the variations mentioned. Measuring only where values are low and coorelating that with ice cores is not a valid way to assess global concentration.
Jim, CO2 is only badly mixed in places near huge sinks and sources. That is in the first few hundred meters over land.
Even over land: flight measurements over the Rocky Mountains once over 500 meter height, one does find the same CO2 levels as at Mauna Loa some 6,000 km away:
In 5% of the atmosphere by weight, near surface over land, CO2 is chaotic. In 95% of the atmosphere, CO2 is well mixed, besides relative small differences due to the seasons, even when 25% of all CO2 of the atmosphere gets in and out over a year…
Here an example from a modern measuring station at Linden/Giessen, taking samples of CO2 and other gases over GC each half hour. That station is only a few km from the place where a long series of three CO2 samples a day with chemical methods were taken in the past (1939-1941). That series was the main base of the 1942 “peak” in CO2 in the compilation of Ernst Beck. All data are direct, unfiltered measurements, including local outliers:
I suppose that everybody here agrees that we shouldn’t measure temperature trends in the middle of towns. But CO2 measurements in the middle of forests should be used? I don’t see any reason why we should do that.
“In 5% of the atmosphere by weight, near surface over land, CO2 is chaotic. “
You realize that you are your own worst enemy don’t you?
Gravity alone means that CO2 will have a gradient that is elevation dependent. The majority of the CO2 anywhere will be closer to the surface than at height. Yet you say that the CO2 near the surface has significant variation while that at height does not. That means that your guess at the total CO2 has significant measurement error that you refuse to admit to. In addition, it is the CO2 near the surface that will provide most of the absorption of LWIR from the surface and will then have a more significant impact on an GHE effect.
“In 95% of the atmosphere, CO2 is well mixed,”
How do you know this if you have measurement uncertainty of the CO2 near the surface? If you have measurement uncertainty where the density gradient is the highest then that will carry over to any overall guess at the total amount.
You continue to provide magic thinking and hand waving to try and ignore the measurement uncertainty that obviously exists in your data. That *is* typical of climate science so you are not alone in ignoring measurement uncertainty.
Tim, I have used Modtran to calculate the effect of 1000 ppmv CO2 in the first 1000 meter of the atmosphere and the effect was very small: 0.32 W/m2 less emissions towards space.
As Modtran calculates over the full globe, which is 70% water where there is no mixing problem, the 30% over land is good for 0.1 W/m2 if (and only if) there is a bias of 600 ppmv over land in the first 1000 meter.
Even that is overblown: the observed bias over land at e.g. Giessen is about 40 ppmv at ground level. Simply negligible for its GHG effect or the measurement error. And of no interest for the trend in GHG level.
“As Modtran calculates over the full globe, which is 70% water where there is no mixing problem”
So are you now claiming that gravity doesn’t generate density differences with altitude? Are you now claiming that there is no wind near the surface of the water? Are you now claiming that evaporation from the surface of the ocean doesn’t generate convective effects?
This all strikes me of the climate science meme that “averages” can adequately give a full explanation of the physics of the biosphere. A meme that simply can’t be physically justified.
Tim, the discussion is about CO2, which shows very little difference from the surface up to 30 km height in atmospheric level (that is a ratio, not an absolute figure), only a lag of a few months for changes near the surface. CO2 levels at Cape Kumukahi at 7 meter above sea level and Mauna Loa at 3400 meter are the same, besides a small lag
The layer of air where CO2 is chaotic is only near the surface over land near huge sources and sink, like vegetation. That is in about 5% of the total atmosphere by weight. Measure CO2 there, and you can have any CO2 level that you (don’t) like. Except if there is sufficient wind, then the levels get asymptotically towards the “background” level.
Here for the same station at Linden/Giessen as pictured before with extreme outliers under inversion but now at increasing wind speed:
Again, in 95% of the atmosphere by weight, one does find a difference of maximum 5 ppmv in yearly averages and even that difference is because of the fact that 90% of all human emissions are in the NH and need some time (about 2 years) to reach the South Pole.
What is missing?
Your logic is … not.
If humans are the only ‘net source’, then 150,000 years ago the ‘net sinks’ were doing a very poor job of following being able to follow your logic.
Humans aren’t the only possible net source. The ocean can sometimes be a net source too. The land can sometimes be a net source too. It’s just that they haven’t been over the period 1850-2024.
The carbon cycle 150,000 years ago has no problem with my logic because it behaved in a manner consistent with the law of conservation of mass just like it behaves in a manner consistent with the law of conservation of mass today.
As I said before, the Baltica Sae is a net source.
https://link.springer.com/chapter/10.1007/978-3-642-19388-0_5
As I said before, the Baltica Sae is a net source.
https://link.springer.com/chapter/10.1007/978-3-642-19388-0_5
Just because the Baltic Sea is a net source does not mean that the entire ocean is a net source.
Didi I say/write that?
No, so your answer is obsolete.
Did I say/write that the Baltic Sea wasn’t a net source?
No, so your answer was an irrelevant deflection and diversion.
You start your entire premise intimating that humans are the only significant net source.
Be honest or go away.
Somehow a 30% increase in greenery doesn’t require some increase in plant respiration, i.e., CO2, in order to grow.
I assume you were wanting to respond to me. I’m not intimating here. I’m full on saying that the law of conservation of mass indisputably and unequivocally says that the CO2 increase in the atmosphere is nearly 100% the result of humans.
And in case you meant to say “assuming” it to be true and not “intimating” it then I’ll nip that in the bud right now as well. I’m not assuming anything. I’m applying the law of conservation of mass to the known mass flows within the carbon cycle.
I get it. The law of conservation of mass is massively triggering to many commenters here. Despite the contrarian challenges it is fact real. It be dishonest of me to reject or ignore it.
And before anyone gets the idea that I’ve said something that I actually didn’t then make the following known. I didn’t say that humans are the only net source of CO2 for all of Earth’s past or even humanities past. I didn’t say scientists have a perfect accounting of all of the flows of carbon in the carbon cycle. I didn’t say that the minutia of details is settled. There are a lot of things I didn’t say here. We can save a lot of time here if everyone avoids strawman arguments and instead focuses on arguments that scientists are actually making.
Nobody is denying that conservation of mass is an appropriate law.
What people are trying to tell you is that you do not have sufficient data to properly calculate anything.
If you do not have a comprehensive category list with measured quantities, then you are guessing.
Guessing is not science, it is opinion.
“I get it. The law of conservation of mass is massively triggering to many commenters here.”
What is triggering is you trying to use the overall conservation of mass as evidence of the functional relationship among the various process factors that impact how that mass is processed and the impacts of those process on the biosphere.
You keep trying to ignore the fact that you have nothing but guesses at the impacts of the functional relationship among the factors and you cover that up with a red herring argument.
You disagreed with me earlier and now you are agreeing.
Kewl
It depends on the topic. I might agree with you on some things and not others. It’s not a one-way street for me.
Because your comment in this particular subthread lacks context I have no idea what you are talking about so I can’t say either way if I agree with you or not. If you reveal the context I can then inform you if I agree or not.
For conservation of mass you have to know *ALL* sources and sinks with enough certainty to identify the differences you are trying to find. As usual climate science is claiming to be all-knowing.
Tim, you don’t need to know one natural CO2 in/out flux, because we know the difference between all natural ins and all natural outs quite exactly:
That is what we measure as increase in the atmosphere and what human emitted over the years: quite accurately known from taxes on sales and burning efficiency.
Where that difference goes: in the oceans and/or biosphere is roughly known, based on O2 and other measurements. In all cases, both are net sinks for CO2, not net sources. In all cases, the errors in the measurements are a lot smaller than the calculated uptake.
Based on measurements roughly for 2020:
Human in: 10 PgC as CO2, calculated.from sales (taxes).
Atmosphere: 5 PgC (temporarily) remaining, measured.
5 PgC absorbed in nature (wherever that may be):
Biosphere: 2.5 PgC uptake, based on O2 changes.
Ocean surface: 0.5 PgC uptake, based on DIC measurements.
Deep oceans: 2.0 PgC uptake, based on tracers and to close the carbon mass balance and a lack of other fast, large sinks (not other sources!).
“That is what we measure”
Measurements ALWAYS have measurement uncertainty. You are asking us to believe that all your data is 100% accurate.
“Human in: 10 PgC as CO2, calculated.from sales (taxes).”
Which means that an ASSUMPTION is being made about the input and output functional relationship. ASSUMPTIONS *always* have measurement uncertainty – *always*!
This applies to each factor you have listed.
You haven’t given a single measurement uncertainty interval for anything you’ve listed.
Why is that?
Tim, I have several times now given the measurement errors, but all you do is avoiding a real discussion about the essence of the figures.
That essence is that human emissions, including the measurement errors are way higher than the increase in the atmosphere, including the measurement errors.
Thus humans are the one and only cause of the over 100 ppmv increase in the atmosphere since 1958, because humans added over 200 ppmv over the same time span.
No matter if the errors in one year were 10% or 20% or 50% for both measurements involved, as sample/calculation errors in one year are compensated in the next year(s).
Only a systematic bias will accumulate over time, but for human emissions that is most likely an underestimation of the emissions. Not an overestimation…
For CO2 measurements, a systematic bias is very unlikely,
“Tim, I have several times now given the measurement errors, but all you do is avoiding a real discussion about the essence of the figures.”
No, you have not. Even your quote of current CO2 being at 425 ppmv or that the 100ppmv increase do not include statements of what the measurement uncertainties are that are associated with those values.
It’s not obvious that you have even the most basic understanding of metrology – e.g. your statement that all uncertainty will cancel out from year to year, i.e. all measurement uncertainty is random, Gaussian, and cancels.
Literally NO ONE that has ever been involved with measurements that carry criminal or civil liability if inaccurate will accept a simple statement of “adequate accuracy”.
“That essence is that human emissions, including the measurement errors are way higher than the increase in the atmosphere, including the measurement errors.”
If you can’t state what the measurement errors are then how can you know what is and what isn’t happening? This is truly nothing more than magic thinking and application of “trust me”.
“No matter if the errors in one year were 10% or 20% or 50% for both measurements involved, as sample/calculation errors in one year are compensated in the next year(s).”
This is just one more confirmation that you simply do not understand the basic concepts of metrology. Uncertainty doesn’t cancel from year to year when different things are being combined. They ADD.
“100 ppmv increase”
If your measurement this year was 500 +/- 10 and for next year it is 600 +/- 10 then the actual difference can range from 490 for year one to 610 the next year. That means your measurements suddenly give a difference with a +/- 20 ( max diff = 610-490 =120, min diff 590-510 = 80) uncertainty instead of +/- 10 for a single measurement. For the 3rd year your measurement uncertainty will increase to +/- 30, i.e. 700-500 = 200 +/- 30.
The uncertainty in the difference will grow and grow for every year you add to the series. Simple metrology.
That is patently false. The beauty of algebra is that we can represent unknowns with variables and then solve for those variables using equations like the law of conservation of mass (LoCM)
The algebra in association with the LoCM tells us that we only need to substitute real numbers for 2 of the 3 variables (ΔM, Min, Mout) to solve for the 3rd. For example, if you know ΔM and Min then you can solve for Mout.
The LoCM is one of the most powerful tools we have when analyzing the carbon cycle.
“That is patently false. The beauty of algebra is that we can represent unknowns with variables and then solve for those variables using equations like the law of conservation of mass (LoCM)”
Bullshite! The operative word here is “unknowns”. That means there is uncertainty somewhere in the “algebra” calculations.
“real numbers”
So you *do* know the factors? Then why not tell us the functional relationship that shows how they combine, including the weighting factor for each?
The question was what percentage of the total does each represent? All you given us is magic thinking and hand waving as an answer.
If Total = ax + by +cz whre a/b/c are weighting constants and x/y/z are variables how do you solve the algebra if you don’t know a/b/c *and* two of the variables?
It is the TOTAL that is of actual interest and you apparently can’t tell us that.
The usage of variables in algebra and solving for those variables is not “Bullshite!”.
The law of conservation of mass is not “Bullshite!”
Given other sources, you do not have constant variables.
Your premise: “IF people are the only source” has been shown to be incorrect, so you should just walk away.
It doesn’t matter. You handle other unknown sources/sinks as a variable in the equation.
ΔM = Σ[Mk_in_i – Mk_out_i, 1 n] + (Mu_in – Mu_out)
In the above equation the subscripts ‘k’ means known and ‘u’ means unknown.
Since the carbon cycle is considered a closed system we set ΔM = 0.
And if Σ[Mk_in_i – Mk_out_i, 1 n] = 0 that tells us that (Mu_in – Mu_out) = 0 as well.
And if the flow Mk_out_i is only going to Mk_in_j for all (i,j) then we know that the flow from Mu_out to Mk_in_i for all i must be 0.
In other words under the above assumptions the carbon in the unknown catch-all reservoir may be moving around in that reservoir, but it is not moving out of that reservoir and into one of our known reservoirs.
According to Friendlingstein et al. 2024 ΔM and Σ[Mk_in_i – Mk_out_i, 1 n] = 0 are very close to zero with all flows being accounted for meaning that the total of all unknown sources is insignificant.
That’s not my premise.
You keep avoiding the *real* issue. The *real* issue is not total mass.
The *real* issue is the processes involved in M_in and M_out. It is those processes and their functional relationship that determine the impact on the biosphere.
When you can give us the processes and their functional relationship for each factor, M_in and M_out, then perhaps there can be a discussion of the “real” issues. Till then you are just flapping your gums.
What is bullshite is *YOU* claiming you know what all but one of the “unknowns” are plus their weighting factors in a functional relationship.
If you don’t know the unknowns then no amount of algebra will help you.
The law of conservation of mass is useless unless you *know* the values of the unknowns and their weighting factors.
Are you omniscient? That seems to be a common malady among climate scientists.
Carbon is not CO2.
CO2 is composed of carbon. It is therefore a carrier of carbon. If CO2 is in the reservoir then carbon is in the reservoir.
CO2 is a trace gas, carbon too?
No.
Yes it is. So is CH4, HCFC-x, CFC-x, or any other gas species in which carbon is bonded.
Carbon is C, simple as that.
Right. So it should be easy to recognize that CO2, CH4, CFCs, HCFCs, etc. are carbon based gas species. No?
Here is a question for you. How much carbon do humans sequester each day? Does that enter into any calculation?
Those taking off catalytic converters from their autos (illegal in many places) are sequestering CO2. while this may not be a large contributor it *is* a contributor and should be recognized as such. Just ignoring it is not “scientific* but is typical of climate science.
How many ponds across the land surface have algae in them? If temps are warming this will go up. Doesn’t algae sequester CO2? How is this identified and included in CO2 sink calculations. Again, if you don’t recognize *all* factors and just assume they are insignificant then how “scientific” is that?
Never heard of the phosphor and nitrogen balance in agriculture? That simply is used to make comparisons of quantities and transfers easy to follow, as the elements are conserved as mass, no matter in what molecule they are present and/or moving…
The issue isn’t the total mass of each element. The issue is how they relate and what are the processes they are involved in. You simply can’t know what the total relationship between phosphor and nitrogen in the global soil makeup since it is highly dependent on soil condition. I can’t find anywhere that gives any kind of a measurement and measurement uncertainty for that on even a regional basis let alone a global basis.
Carbon is C, not CO2. It is an element, not a molecule.
Conflating them is done to pursue confusion and alarmism.
No offense, but duh. It’s a good thing I never said carbon was a molecule.
I’m not the one challenging the fact that CO2 is a carbon based molecule.
https://www.academia.edu/121102484/Carbon_cycle_modelling_and_the_residence_time_of_natural_and_anthropogenic_atmospheric_CO_2_on_the_construction_of_the_Greenhouse_Effect_Global_Warming_dogma
I’m not sure what the point of this publication is. The conclusion violates the law of conservation mass. As part of justifying this violation of the LoCM the authors conflate residence time with adjustment time like many of the other LoCM violating publications.
Krishna, I have had discussions with Segalstad in the early 2000’s. His work from 1998 is completely outdated and refuted with a lot of measurements in the atmosphere since then.
Basically the article says all the cliimate models are fantasy.
There we agree:
https://www.ferdinand-engelbeen.be/klimaat/oxford.html
The conservation of mass includes the ocean outgassing. If the ocean is warming and outgassing more C12 than C23 then the ratio of C12/C13 will change unless the uptake of the ocean also increases at the same time – which makes no sense if it is warmer.
The ocean is a net sink of C13 and a net source of C12.
Equilibrium dynamics shift the flow rates.
According to such scheme, the ocean surface acts as a mass spectrogram…
Never heard of such a theory…
What is known (and measured) is that the ratio between 13C and 12C slightly gets smaller when CO2 transfers from water to air (-10 per mil) and again from air to water (-2 per mil) giving a net drop of -8 per mil, as long as the ins and outs are equal.
That are fractions of a percent, in each direction, not total quantities. As the average CO2 transfer in quantity is from the atmosphere into the oceans, both 13C and 12C increase in the ocean surface…
Tim, the oceans are absorbing some 2.5 PgC more as CO2 than they are outgassing… The effect of warming oceans since the LIA is a meager 13 ppmv increase in equilibrium with the atmosphere (at around 295 ppmv). We are now at 425 ppmv, that is way above the dynamic equilibrium of the sea surface with the atmosphere at current SST. Thus the (measured!) net flux of CO2 is from the atmosphere into the ocean surface (and deep oceans), not reverse: DIC (dissolved inorganic carbon, that is CO2 + bicarbonate + carbonate) in the ocean surface is increasing, while the pH is slightly decreasing…
https://tos.org/oceanography/assets/docs/27-1_bates.pdf Figure 2 and Table 3.
Moreover, there is a huge drop in 13C/12C ratio both in the atmosphere as in the ocean surface, where the calcification 13C/12C ratio in coralline sponges follows the ratio in the atmosphere with some 4 years (thus just reverse of what is alleged by Jennifer)…
Not a single value you give has an associated measurement uncertainty interval – meaning you want us to believe they are 100% accurate.
There is simply *NO* way I am going to buy into that magical thinking. I’ve had over 60 years worth of making measurements behind me, including for things affecting the safety of users.
Come back when you can give us some measurement uncertainty intervals that are reasonable so we can judge whether you are able to actually measure the differences you are stating.
Of course the figures are not 100% accurate, But they are more than accurate enough to show that the new hypothesis of Jennifer and Ivan can’t be true…
For the CO2 measurements in ice cores, that is 1.2 ppmv (1 sigma) at a level of 280-380 ppmv. From 1958 on 0.2 ppmv (1 sigma) in direct measurements.
For the isotopic composition: 0.05‰ for δ13C levels in ice cores for a drop of over 2‰ since 1850.
I have not searched for the accuracy of δ13C in the atmosphere, but I suppose that it only will be better (easier to obtain) than in ice cores air.
For the isotopic composition of the sponges:
External precision (2σ) of δ13C mesurements based on multiple analyses (N = 87) of standards NBS 19 and IAEA CO1 is ±0.04‰
See further chapter 3.1.3 for ice core measurements in:
https://agupubs.onlinelibrary.wiley.com/doi/full/10.1002/jgrd.50668
and
https://agupubs.onlinelibrary.wiley.com/doi/full/10.1029/2001GC000264
for the sponges…
The error margins thus are way smaller than the natural variability and certainly the enormous drop after 1850, fully caused by fossil fuel emissions.
I think that you are confusing measurement uncertainties with the less than perfect correlation with proxies and effects.
Sampling issues aren’t mentioned. What happens to the reliability of CO2 ice-core measurements when a massive melting event (as happened recently in Greenland) wipes out all the snow and much of the firn, and then is reburied by new snow?
Clyde, CO2 measurements in ice cores are direct measurements, not proxy’s. Measured with the same kind of (or even sometimes the same) equipment as direct measurements in the atmosphere. The only drawback is that they are averages of less than a decade (Law Dome), up to 560 years (Dome C).
Melting may happen and that stops the diffusion of air/CO2 down the pores, and increases the CO2 level near the melt layer. That is accounted for in the measurements (it influences the difference in age of the enclosed gas bubbles vs the ice age).
Happens more in Greenland ice than in coastal Antarctic ice and not at all in much colder Antarctic inland ice.
“Measured with the same kind of (or even sometimes the same) equipment as direct measurements in the atmosphere.”
All instruments have a measurement uncertainty. What is the measurement uncertainty of these instruments?
0.2 ppmv (1 sigma) for the NDIR method for CO2 measurements.
0.05‰ (1 sigma) for δ13C levels in air for mass spectrometers.
More that accurate enough to monitor the increase of 100 ppmv since 1958 and the 1.0‰ drop since 1978 at Mauna Loa and the South Pole:
https://scrippsco2.ucsd.edu/graphics_gallery/isotopic_data/mauna_loa_and_south_pole_isotopic_c13_ratio.html
Since last year, the NDIR method was replaced after 65 years of good service by another method at Mauna Loa, which should be even more accurate than the NDIR method.
“0.2 ppmv (1 sigma) for the NDIR method for CO2 measurements.
0.05‰ (1 sigma) for δ13C levels in air for mass spectrometers.”
How many measurements will it take with a 0.2ppmv measurement uncertainty for the total measurement uncertainty to overtake the differences you are trying to identify?
Are you still going to claim that all measurement uncertainty is random, Gaussian, and cancels?
https://scrippsco2.ucsd.edu/assets/graphics/pdf/c13_mlo_spo.pdf?1736161565820
Are CH4 sources included in the process?
After CH4 oxydation, you have CO2 and 2H2O
Consider that auto emissions are considered to be a significant factor in human CO2 production. Yet CO2 production from a fossil fuel autois highly dependent on the efficiency of the engine and associated catalytic converter. So exactly what is the total efficiency of all autos in the world? Since engines and catalytic converters *do* degrade over time that is not a static target plus the fact that the degradation typically produces *less* CO2, not more CO2.
Tim, even remaining unburned fuel gets oxidized after some time, except black carbon and other half burned stuff, but that is peanuts compared to total fuel use (or you wouldn’t drive long with a dark plume behind your car)…
“im, even remaining unburned fuel gets oxidized after some time,”
So what? It depends on WHEN that happens as far as its contribution . Does it get burned when sinking capability is at maximum or at minimum? Using annual averages can’t tell you that. Sinking and sourcing are *time* functions, not constants determined by averages.
You keep on trying to simplify a complex problem. That is typical for climate science. It’s why you see so much “averaging” instead of actual functional relationships being analyzed. Climate science doesn’t even recognize that a daytime temperature profile (a sine wave) and a nighttime temperature profile (a decaying exponential) does not ‘average” out to (Tmax + Tmin)/2!
You can’t even tell us what the total mass of CO2 in the biosphere with an appropriate uncertainty interval let alone all the various factors (which themselves are at least time based functional relationships) and their weighting as part of a comprehensive functional relationship. And we are supposed to believe that your attribution factors are remotely accurate? I would never sign off on a bridge design document so full of “averages” with no measurement uncertainties for anything.
Tim, have you ever heard about the signal to noise ratio?
You are over-focused on short term changes and short term errors and other items that don’t matter at all.
It does hardly matters that some fuel is sold and only used 10 years later.
It doesn’t matter at all how much carbon is in the biosphere or in the (deep) oceans.
It doesn’t matter how large the natural inflows and outflows over a year are and how they changed from one year to next or over the years, nor their variability. Only the (small, temperature induced) net trend of the natural carbon release/uptake matters.
What really matters is how much human induced CO2 gets one-way into the atmosphere over the full period of measurements and how much the CO2 level in the atmosphere increased. Including the margins of error over the full period.
That tells us everything about the cause of the increase and its (possible) effect as GHG (but that is a complete different topic).
Human emissions were over 200 ppmv 1958-2025, based on sales.
Errors (all one sigma):
Calculation error +/- 10%, not cumulative:
+/- 0.15 ppmv in 1958
+/- 0.5 ppmv in 2025
Land use changes, cumulative:
+0.5 ppmv in 1958 (without the period before 1958)
+50 ppmv in 2025
Underestimation of sales, cumulative:
+0.15 ppmv in 1958
+22 ppmv in 2025
Overall trend, including error margins:
0 ppmv -0.15 / +0.8 ppmv in 1958, ignoring pre-1958 sales.
200 ppmv -0.5 / +72.5 ppmv in 2025
The atmospheric increase was over 100 ppmv, based on direct measurements:
Measurement error, not cumulative:
+/- 0.2 ppmv in 1958 and 2023 (even better since 2024).
Yearly averages based on over 300,000 samples per year per station in 1958 up to over 2 million samples per year in 2025.
Spread in the measurements due to local factors, excluding seasonal changes, not cumulative:
Barrow: +/- 5 ppmv
Mauna Loa: +/- 2 ppmv
South Pole: +/- 0.5 ppmv
Maximum difference between stations in yearly averages, not cumulative:
1 ppmv in 1960.
5 ppmv in 2025.
Maximum error and bias for 5% CO2 over land (not cumulative):
Bias in averages (+40 ppmv, modern, Linden/Giessen):
+2 ppmv
Spread in daily variability:
Historical +/- 68 ppmv (Giessen, mid-west Germany, 1939-1941 wet chemical methods):
+/- 3.4 ppmv
Modern +/- 20 ppmv (Linden/Giessen):
+/- 1.0 ppmv
Overall trend, including all kinds of possible errors:
305 ppmv -7.2 / +9.2 ppmv in 1958
415 ppmv -11.2 / +13.2 ppmv in 2025
With an average trend of 110 ppmv .
Simply said: human emissions are the main cause of the increase in the atmosphere at about twice the measured increase, even including all kinds of possible errors. Nature is a net sink for the difference, wherever that may be.
Those who are looking at short time variability (seasonal, yearly, year by year) are fooling themselves by high correlations between temperature rate of change variability and CO2 rate of change variability, while there is near zero trend in the temperature rate of change and human emissions show twice the trend of what happens in the atmosphere in rate of change and in total added CO2…
“Tim, have you ever heard about the signal to noise ratio?”
I lived with it for my entire career. From error correction in T1 digital carrier systems to path loss and signal detection in microwave telephone links.
“You are over-focused on short term changes and short term errors and other items that don’t matter at all.”
You haven’t understood a single thing I have tried to teach you about metrology. I am *not* focused on short term changes and short term errors. I *am* focused on the increase in measurement uncertainty as it adds up OVER TIME, especially LONG PERIODS OF TIME.
You are the same as most climate scientists I have had this kind of discussion with. You and they simply don’t understand that measurement uncertainty is *not* random, it is *not* Gaussian, and it does *NOT* cancel over the long term.
You apparently didn’t even bother to actually read and comprehend my example to you of how subsequent years of 500 +/- 10, 600 +/- 10, and 700 +/- 10 adds up to a measurement uncertainty in the difference of 200 +/- 30. It has nothing to do with the individual measurement uncertainties or the measurement uncertainty of individual measurements, it has to do with the measurement uncertainty of the differences between the beginning and end OVER TIME. There is nothing short term about this.
I have never seen a climate study that used serious time analysis to evaluate a “climate” component. Just more and more averages along with linear regression.
A real time series analysis would at least begin with trying to make it stationary. This many times begins with determining the 1st differences. See this site:
https://people.duke.edu/~rnau/411diff.htm
Identifying the need for a signal to noise ratio requires an accurate description of what the signal actually is. This is needed so one can start to identify the noise/interfering contribution to the measured signal.
In too many climate science analysis of measurements, averaging is declared to be a method for reducing the signal to noise when it is really used for obscuring the variance in the actual signal.
The variance is a measurement of uncertainty in the true value. It should not be minimized and should quoted along with the quoted mean of a probability distribution. If averaged again one must propagate the uncertainty.
climate science Rule 2: averaging decreases measurement uncertainty
climate science Rule 3: averaging increases resolution of measurements
And of course Rule 1: all measurement uncertainty is random, Gaussian, and cancels.
2 ppmv CH4 in the atmosphere.. peanuts as mass, but with relative more influence on the GHG effect.
10X
I haven’t had time recently to write up this issue, but I think I have a compelling argument to dismiss it. Stay tuned.
Well damn. Some real science.
Taking CO2 to new communities
Mykhailo Viktorovych Polyakov, 24, reached the northeastern shore of the [North Sentinel] island at 10 a.m. on March 29, according to the police. He scanned the land with binoculars, but saw no one. So he climbed ashore, left the Diet Coke and the coconut there, took sand samples, and recorded a video, the police said.
https://www.nytimes.com/2025/04/04/world/asia/north-sentinel-island-us-man-arrested.html
Isn’t it astonishing that CO2 that is claimed to have an atmospheric residency time of hundreds if not thousands of years shows such a seasonal variation as measured at MLO?
This is incorrect.
The residence time is on the order of about 5 years.
It is the adjustment time that is on the order of hundreds of years.
Those are two different concepts.
with a residence time ‘on the order of hundreds of years’, and net sinks abound, it’s a good thing humans are sourcing CO2.
logically, the earth would run out in short order without human intervention. undeniably sound logic.
I know that. I should have added a /s, but lots of “scientists say” precedes the hundreds or thousands of years in the media reports. And they are reportedly saying the levels of CO2.
When you see “hundreds or thousands of years” they are talking about the adjustment time; not the residence time. These are two different concepts that should not be conflated.
No. They are not doing that. They are promulgating alarmist rhetoric.
Can you post a link where they are doing that so that we can review it together?
Different processes at work: seasonally: all temperature – photosynthesis – decay – digestion. Hardly influenced by the amount/pressure of CO2 in the atmosphere. Leading, together with the oceans, to a residence time (RT) of around 4 years.
That doesn’t remove one gram CO2 from the atmosphere, only moves 25% of all CO2 in the atmosphere per year between oceans, atmosphere and vegetation and back.
The removal rate (“adjustment time”), that is the time needed to remove any extra injection of CO2 above the dynamic equilibrium with the ocean surface, Tau, is about 50 years.
Tau is the time needed to reduce a one-time injection of CO2 in the atmosphere (of whatever source) to 1/e (about 37%) of the initial injection.
The hundreds to thousands of years is based on the faulty Bern model of the IPCC…
Thank you. A concise explanation, better than mine. Much.
Marvelous!
This is so well done —
— and may well even turn out to be true meaning ‘complete’, IDK) —
… that it could probably be used in the General Chemistry (college freshman / HS AP) courses, under ‘Kinetic Isotope Effects’ …
… not to mention all the higher courses (geochem / biochem etc.) based thereupon.
According to the IPCC, the oceans have only warmed by about 0.03C. How much outgassing should that cause?
Beyond that, if you add up all the fossil fuels that have been burned in the last 100 years or so, it should have produced enough CO2 to account for 2 to 3 times as much increase in atmospheric CO2 levels, than have actually been observed.
How much outgassing should that cause?
Not much. Observe the bubbles in your drink and the difference between it and the ambient temperature.
CO2 bubbles at ocean surface? 🤣
Bubbles in drinks are based on high pressure
Have you seen how big the oceans are, and all that spray and wave action? It doesn’t take a lot to make a lot.
Re “… oceans have only warmed by about 0.03C.”
And are very cold at ~ 6 oC, because [Pleistocene Ice Age etc.] several millions years of cooling down to -4000-m average ocean depth.
But that has little-to-nothing to do with the ‘mixing layer’, i.e. the top ~ 100-m that is relevant to anything happening on the sub-millennial timescale (Holocene). This topmost layer is around + 21 oC (~ 70 oF) in the main ( < ± 65 degrees latitude ) wherein the ~ + 0.5 or maybe +1.0 oC post-LIA warming has occurred, according to ARGO plus.
It is quite unfortunately that this is already published, while there is an ongoing discussion on the 13C/12C origin between Jennifer and the CO2 Coalition, as result of the publication of our work on the origin of the CO2 increase…
There are a lot of fundamental flaws in the above reasoning, here a few topics to begin with:
That are already several differences we have with the work of Jennifer and Ivan…
Sorry my reply should be in general, not your question.
The warming oceans are only good for some 13 ppmv CO2 in the atmosphere since the Little Ice age, according to the formula of Takahashi, based on near one million seawater samples:
(pCO2)seawater at Tnew = (pCO2)seawater at Told x EXP[0.0423 x (Tnew – Told)]
The outgassing occurs on the surface so it is the surface temperature that matters; not the bulk temperature.
Anyway this question can be answered with the [Takahashi et al. 1993] equation d[ln(C)]/dT = 0.042 which says that about 400 ppm in the atmosphere than ocean will have a change in net outgassing equivalent to 16 ppm given 1 C change in surface temperature.
This is not saying that a 1 C change in temperature will cause the ocean to outgas the equivalent of 16 ppm. It is saying that the change in outgassing is equivalent to 16 ppm. So if the net outgassing is -149 ppm (net sink) then adding 16 ppm to that is -133 ppm (still net sink).
Bingo. The carbon mass that humans injected into the atmosphere also got dispatched into the land and ocean increasing their mass as well. The law of conservation of mass therefore says in no uncertain terms that neither the land nor the ocean is the reservoir that acted as the source of carbon. In fact, they acted as the sink that prevented the atmosphere mass gain from being higher than it already is.
So now we have to put up with the idiocy of applying conservation of mass to a chaotic, dynamic, multiple coupled energy system.
I need a beer. Oops CO2….
You don’t think the law of conservation of mass applies to a chaotic, dynamic, multiple coupled energy system?
Total = ax + by +cz where a/b/c are weighting factors and x/y/z are variables. It is the total that is of prime interest yet you can’t seem to tell us the weighting factors let alone the measurement uncertainties associated with x/y/z.
The chaotic, dynamic, multiple coupled energy system will see a/b/c change as time goes on. So will x/y/z.
Each of those changes will impact what the TOTAL is. And apparently you can’t tell us what that is.
Conservation of mass applies to chemical reactions.
You don’t think chemical reactions happen in a chaotic, dynamic, multiple coupled energy system?
According to the IPCC.
Gasp, be still my racing heart.
How is it the oceans have only warmed 0.03 C but the atmosphere has warmed by 1.5 C give or take.
The oceans, covering 71% of the planet’s surface, is a massive heat sink. If the temperature difference is that great, the oceans are sucking in multitudes of joules from the atmosphere causing it to cool. The thermal mass of the oceans is tremendously greater than the thermal mass of the atmosphere.
As far as the burning of hydrocarbon fuels and coal and CO2 levels, yes. I agree.
The devil is in the details. Jennifer demonstrated that we don’t understand even the simplest components of the climate system.
The annual variation is 6 ppm according to the graph. This is generally assumed to be due to the variation in land area and vegetation growth and death in the northern hemisphere versus the southern hemisphere as the seasons progress. But one degree of temperature variation is about 10 ppm CO2 content variation in the air above that sea water IIRC Henry’s law and all that…..so one might also come to the hypothesis that the CO2 variation is caused by ocean surface warming and cooling as the seasons progress over the different amount of ocean area of the northern and southern hemispheres. Sorry coffee time…someone else can do the back of napkin calcs…
One can know the cause of the CO2 variations over the seasons and on long term: CO2 changes and δ13C changes parallel each other is the CO2 is from the oceans and oppose each other when caused by current of fossil organics. The biosphere is leading:
Moreover, ocean temperature changes give small O2 changes, CO2 uptake or release by/from the biosphere gives stoichiometric changes in O2 in opposite direction, which is largely the case for seasonal changes:
Thanks for the reply Ferdinand. CO2 in the surface water samples reflects the CO2 in the atmosphere above pretty well. The blue line variations are likely due to the different surface temperature at which the sample was taken.
I proposed that hypothesis some time ago.
I do not accept the MLO explanation that it is all vegetation growth and decay over the seasons.
I also suggested ocean surface temperature readings at various distanced from the measurement site.
Also, the volcanos in the region. No explanation why those are not accounted for, except MLO had to move 200 miles away due to Kilauea erupting.
The Mauna Loa observatory started reporting atmospheric CO2 data in March 1958 and continues to do so today. There was a temporary move as reported by NOAA: “Due to the eruption of the Mauna Loa Volcano, measurements from Mauna Loa Observatory were suspended as of Nov. 29, 2022. Observations from December 2022 to July 4, 2023 are from a site at the Maunakea Observatories, approximately 21 miles north of the Mauna Loa Observatory. Mauna Loa observations resumed in July 2023.”
What is your source for a 200 mile move?
Except for plate tectonics recycling limestone and iron into hydrocarbons all carbon based life on earth would have gone extinct a billion years ago.
Anton Petrov just published a video about a “study” indicating that plate tectonics are a result of an impact with a big rock. Magma plumes are not convection, rather impact “damage”. https://www.youtube.com/watch?v=LFfRvyoUeuA
If so, our presence is the direct result of a single low low low probability event. Is it 4:20?
There is a hypothesis that the moon is the result of such a collision.
My opinion (worth as much as the paper on which this is written) is the plate fragmentation is merely the result of cooling molten surface (rock). Lot of examples showing how this happens. Cooking gives real visuals.
Life in the oceans turns CO2 into shell. Shell is inedible and insoluble and rains down upon on the ocean floor where it is lost for millions of years.
And subducted and under extreme heat and pressure transforms into other materials.
Millions of years ago 3 foot dragonflies without lungs absorbed enough oxygen to fly. The atmosphere was 35% oxygen. Now it is 20%, barely enough for a canary. What happened to that oxygen? Life turned it into fossilized carbon dioxide. The atmosphere has never been in balance ever since life appeared.
From here is a graph of the last millenium or so of mass of carbon in the atmosphere
What would make the ocean change its fizz over time like that? Centuris of no change, and then just suddenly shooting up exactly in proportion to the carbon we burned?
Your jump is, as usual, to short, correlation is not causation.
Coming out of the Little Ice Age, a period M.Mann tried to hide, earth warmed and CO2 started rising.
And If the propaged CO2 amount of 280ppm at this time is at least questionable.
The increase of maximum 0.8°C (not in Mann’s HS…) is good for maximum 13 ppmv extra CO2 in the atmosphere at equilibrium with the atmosphere.
Over the past 800,000 years, the change between glacial and interglacial periods was not more that 8 ppmv/°C for Antarctic temperatures or 16 ppmv/°C for global temperatures. That is all.
If you calculate the current net sink by nature back to zero sink, then you arrive around 290 ppmv…
See Willis’ calculation at:
https://wattsupwiththat.com/2025/04/04/of-emissions-and-co2/
Nevertheless CO2 increase follows temperature…
Except over the past 175 years…
The influence of temperature is about 5 ppmv/°C for seasonal changes, 3.5 ppmv/°C for year by year changes and up to 16 ppmv/°C for very long term changes like the glacial – interglacial transition with a “speed” of 0.02 ppmv/year…
The current increase is over 100 ppmv for 0.6°C warming since 1958 with over 200 ppmv CO2 release by fossil fuel burning over the same period…
Temperature is good for less than 10 ppmv of that increase.
Correlation is not causation.
…except during the industrial revolution when CO2 was made by humans from the reservoir and injected into the atmosphere because we wanted to produce energy.
…except during flood basalt events when CO2 is outgassed independent of temperature like what happened during the PETM.
There are obviously other ways in which CO2 can increase independent temperature. The two I mentioned above are just examples.
Scientists, as recorded in the journals of the day, recorded CO2 levels comparable to today in 1820.
Where did they record that? If you do measure CO2 in the atmosphere in a forest at night with no wind, you can measure any amount of CO2 you (don’t) like…
Here for a modern rural station in mid-west Germany under inversion, compared to “background” stations over the same days:
I posted this under a previous comment, apologies for repeating but you might not have seen it. Actual measurements exist back to 1812.
“Modern greenhouse hypothesis is based on the work of G.S. Callendar and C.D. Keeling, following S. Arrhenius, as latterly popularized by the IPCC. Review of available literature raise the question if these authors have systematically discarded a large number of valid technical papers and older atmospheric CO2 determinations because they did not fit their hypothesis? Obviously they use only a few carefully selected values from the older literature, invariably choosing results that are consistent with the hypothesis of an induced rise of CO2 in air caused by the burning of fossil fuel. Evidence for lacking evaluation of methods results from the finding that as accurate selected results show systematic errors in the order of at least 20 ppm. Most authors and sources have summarised the historical CO2 determinations by chemical methods incorrectly and promulgated the unjustifiable view that historical methods of analysis were unreliable and produced poor quality results”
https://climatecite.com/wp-content/uploads/Beck-CO2.pdf
There is a newer version of that work, posthumous published by the SCC.
I have had a lot of discussions with the late Ernst Beck in the years 2000-2010, until his untimely death.
While I do admire the tremendous amount of work he has done to recover a lot of old measurements, he didn’t realize that many of these measurements have no value as “background” CO2 at that time: taken near / in forests, growing crops, middle of towns…
Here his latest work:
https://scienceofclimatechange.org/wp-content/uploads/Beck-2010-Reconstruction-of-Atmospheric-CO2.pdf
A comment on that work by me was published by the SCC too:
https://scienceofclimatechange.org/wp-content/uploads/Engelbeen-2023-Beck-Discussion.pdf
Where does this excess CO2 go? Is it of no value in warming the lower atmosphere?
One need the full 70 km air column to see the effect of 100 ppmv CO2 increase everywhere.
I have checked the influence of 1000 ppmv CO2 in the first 1000 meter air in Modtran and it did give a negligible decrease in outgoing IR.
If there is a “real” excess of CO2 near ground that will get mixed with the bulk of the atmosphere with sufficient wind or solar heat introduced turbulence in the afternoon. In general, the high levels at night/morning are from soil bacteria and plant respiration, thus were removed first from the atmosphere during the day…
First question that you should have examined:
“Do you really believe that proxies for establishing atmospheric concentrations prior to, oh, 1700 AD or so have the same accuracy as the scientific instruments employed on Mauna Loa since 1958?”
The repeatability of CO2 measurements in ice cores of samples at the same depth is 1.2 ppmv (1 sigma). The difference between ice cores of the same average gas age is within 5 ppmv. Not bad for knowing the atmosphere over the past 800,000 years.
The only drawback is that the resolution of the enclosed air is an average of 8 years (for the past 150 years) to 560 years (for the past 800,000 years).
1) Repeatability is no indication of accuracy.
2) There currently is on-going scientific debate about gas bubbles captured in ice core samples thousands to tens of thousands of years ago being truly representative of atmospheric gas composition (i.e., relative concentrations of different chemical species) due to effects such as differential gas diffusion rates into the surrounding ice and chemical reactions between the ice and its impurities (such as mineral dust from the atmosphere at time of ice deposition) and the gas species, primarily O2 and CO2, within the gas bubbbles.
3) There currently is on-going scientific debate as to the degree to which gas bubbles in Law Dome ice cores (obtained from a small ice cap on the coast of East Antarctica) is truly representative of average global atmospheric gas composition at the times they were captured. The degree to which the global atmosphere was “well-mixed” at those times is debatable, especially considering that Antarctica is well removed from the vegetative sources of CO2 coming from temperate and tropical latitudes. Then too, there are known mismatches in the derived gas composition of gas bubbles obtained from the Greenland ice sheets compared to those from Law Dome for the same derived historic time of gas capture.
Paleoclimatology proxies (including ice core gas bubbles) are useful indicators, but cannot scientifically be considered as truth.
This is why an uncertainty budget is a required document with verified categories for scientific measurements. It creates a document with necessary items to “accurately” assess uncertainty.
“The degree to which the global atmosphere was “well-mixed” at those times is debatable,”
FE has already admitted that CO2 is *NOT* well-mixed near the surface – meaning it varies based on latitude and longitude.
Much of the arguments being presented seem to be of “say what you need to say at the time” type.
Sorry, as non-English speaker, I still have trouble to see the difference between repeatability and accuracy.
About the accuracy of the ice core measurements at Law Dome, see chapter 3 in:
https://agupubs.onlinelibrary.wiley.com/doi/full/10.1002/jgrd.50668
1.2 ppmv for CO2 (1 sigma).
As far as I know, there is no ongoing scientific discussion about the value of ice cores gas measurements as direct measurements of ancient air. That are direct measurements, not proxies. The only drawback is that they are an average mix of several to many years.
There is a direct overlap of 20 years (1958-1978) between the Law Dome CO2 levels and the direct measurements at the South Pole at a few thousand km of each other.
Greenland ice cores CO2 levels are unreliable due to the inclusion of both acidic volcanic dust from nearby Iceland and sea salt, including carbonates from the surrounding oceans.
Antarctic ice contains much less deposits (somewhat more during glacial periods) and no nearby active volcanoes…
As the current CO2 and δ13C levels in the air at the South Pole follow the changes at near the North Pole (Point Barrow) with a delay of only a few years, I don’t see why that shouldn’t have happened 100 years or 800,000 years ago…
Thus where is the ongoing discussion?
OK, I can accept that, although I notice that your command of the English language in your WUWT postings is exemplary.
Here is just one website the well-defines and illustrates the difference between repeatability and accuracy:
https://new.abb.com/products/measurement-products/measurement-products-blog/are-accuracy-precision-and-repeatability-the-same-thing
and here is what how it summarizes the difference:
“Accuracy
“The accuracy of instrumentation is determined by the difference of a measured value compared to its actual (true) value. As no measurement is 100% exact an element of inaccuracy needs to be considered, hence the reason why accuracy figures are quoted with ‘±’. Ultimately, accuracy measures how close you come to the correct result. Your accuracy improves when your instruments or tools are calibrated properly.
“Repeatability
“Repeatability allows you to measure how close a particular result or set of data is compared to the same measurement, made with the same device or instrument, under the exact same circumstances. In other words, the measurement procedure, observer, device or instrument, testing conditions and location would all need to be exactly the same and testing needs to be conducted over a short space of time.”
This website’s illustrations of the differences between accuracy and precision using the examples of multiple arrows shot onto a target is just excellent IMHO!
. . .
From Google’s AI bot (again, caveat emptor on trusting anything said by any AI bot) in response to entering the search term “debate about the accuracy of bubbles in ice cores”:
“The accuracy of air bubbles in ice cores as a source of information about past climates is a subject of ongoing research and debate, with scientists acknowledging potential limitations while also emphasizing the valuable insights they provide. While ice cores offer a unique and rich record of past atmospheric conditions, including greenhouse gas concentrations and temperature changes, some factors can affect the accuracy of these records, such as bubble closure in the firn zone and post-depositional processes. However, rigorous methods and ongoing research are continually improving the precision and accuracy of these reconstructions.”
[my bold emphasis added]
As to the statement “the only drawback is . . .”, this AI bot totally misses the facts that I previously stated regarding the adverse effects (“drawbacks”?) of long-term differential gas diffusion rates into the surrounding ice and long-term chemical reaction of the captured gas with impurities such as mineral dust present in the surrounding ice.
Yeah, but those 20 years (or even last 100 years) of overlap comparisons DO NOT reflect the very slow gas diffusion and chemical reaction processes (remember, occurring at or below 0 deg-C) that likely take many hundreds of years to become significant . . . but they do eventually become significant.
The main point being that they do contain some mineral deposits capable of reacting with gas captured in air bubbles enclosed by the ice.
Thanks a lot for the reference to the definitions of accuracy, etc… Must put that in memory (not that easy anymore nowadays) and did drop that on my Word sheet of interesting pages…
The AI bot doesn’t quantify the “debate”, which may be about the maximum 5 ppmv difference in CO2 level between ice core gas inclusions for the same average gas age in different ice cores…
While there is an only 20 year overlap between gas inclusions within ice and direct measurements in the atmosphere, there are multiple overlaps between ice cores of quite different average temperature (from -20°C to below -40°C) and enormous differences in snow deposits per year: from 1.4 meter ice equivalent per year at coastal Law Dome to a few mm per year at inland Vostok and Dome C…
That means that migration of CO2 and other gases plays no role in the ice: even not theoretically: the migration of CO2 was measured near a melt layer in the Siple Dome ice core and the theoretical migration did give a broadening of the resolution from 20 to 22 years at medium depth up to a doubling near bedrock, ten thousands of years ago:
https://catalogue.nla.gov.au/catalog/3773250
That was for a relative “warm” ice core (-23°C) with multiple melt layers. Law Dome is slightly “warmer” and a.f.a.i.k has no melt layers.
Even with that migration, the broadening of the resolution over ten thousands of years is not even a problem and for the much colder inland cores (Vostok and Dome C) at -40°C no problem at all, because migration heavily depends of the presence of liquid water pores and temperature…
However there is a “last minute” migration of the smallest molecules just before the bubbles are closed, but CO2 is not one of the victims, O2 and the smaller atomic gases (Ne, Ar,…) partly escape just before bubble closing:
https://tildesites.bowdoin.edu/~mbattle/papers_posters_and_talks/Closeoff_fractionation_EPSL.pdf
If there was substantial migration in ice cores over time, then the ratio between CO2 and temperature of Antarctica ice (~8 ppmv/°C) would fade over 800,000 years migration. That is not the case…
The difference between Greenland cores and Antarctic cores is that in Greenland the deposits are far higher and more important: a mix of ocean carbonates and highly acid (HCl, HF) from nearby Icelandic volcanoes. These can react with each other, both in-situ and especially within the older wet chemical methods.
Law Dome and other coastal Antarctic cores have much more sea salt carbonate deposits than inland cores, but no acids, thus no in-situ CO2 formation and show near the same CO2 levels as the inland cores.
Moreover, the wet measurements are not used anymore for CO2. Only grating of the ice and 100% sublimation for isotopic measurements: no CO2 molecule can hide anywhere…
Seeing the difference is not only a problem of language. Many here have no experience in making measurements and no training in determining their reliability and don’t see the difference.
Let’s discuss accuracy first. Assume I have a voltmeter that reads to the microvolts ± 0.5×10⁻⁷. I get the same reading multiple times from a NIST calibrated reference, say 1.0μv. But what if the true value was 3.5μv. That reading would not be very accurate. More importantly, that is a systematic uncertainty that can not be assessed statistically because every reading will center around 1μv and not 3μv.
Repeatability has two purposes.
Reproducibility uncertainty means changed conditions of measurement. Generally, because you can only make one measurement that can not be repeated. The paper you referenced uses reproducibility because you can’t measure a given sample twice since it is destroyed. However, you can measure 3 slices if the same sample.
Look at the GUM, JCGM 100:2008, Sections 2.15 and 2.16.
Note specifically;
I see you got a downvote simply for explaining some of the most basic concepts of metrology. Meaning someone either is downvoting you based on who you are or they don’t understand the most basic concepts of metrology.
(and you didn’t even get into the definitions of precision and resolution!)
I did give up looking at up or down votes, as these more a question of if the voter likes the answer (or the person who did write a reaction) or not…
Puppy Uppers and Debbie Downers should be recognized by holding your pointer over the count. But that would cost WUWT clicks and eyes, so it won’t happen.
Also thanks for the background, still learning things every day…
What they did at Law Dome is taking multiple slices of the ice at the same depth, that should – theoretically – give exact the same CO2 levels, but indeed these were slightly different (1.2 ppmv – 1 sigma).
That thus is more repeatability than reproducibility…
Don’t think so. The samples are destroyed in order to measure them. Consequently, you can not measure the same thing multiple times. You have single, non-repeatable measurements.
The study showed each of the three parts of a sample were measured by different methods and devices. Those are changed conditions and thus fall under reproducibility.
Repeatability would need a Type B evaluation of repeatability rather than a statistical analysis of a probability. This can be determined from several sources. A gauge study using a reference standard, calibration information from a manufacturer, prior evaluations, etc.
Let me point out that with three degrees of freedom, an expanded uncertainty would require increasing the uncertainty by a factor of ≈3 for a 95% interval.
“Do you really believe that proxies”
They are not proxies. They are air bubbles trapped in the Law Dome ice, and can be analysed with scientific instruments just as air at Mauna Loa.
Besides, there is an overlap period of excellent agreement.
They are proxies. Ice is not static.
Grok says CO2 measured in ice cores is data, “CO2 in ice cores is considered **measured data** by science. The CO2 is trapped in air bubbles within the ice, and its concentration is directly measured using techniques like gas chromatography or infrared spectroscopy. This distinguishes it from **proxy data**, which involves indirect indicators (e.g., tree rings or isotopic ratios) that infer past conditions rather than directly measuring them.
IMHO, you should use a bit more discretion in believing what Grok, or any other AI bot, proclaims. These programs are known to hallucinate and to be just plain wrong!
In any event if you want to follow Grok’s lead and believe that “**measured data**” is automatically considered to be accurate data by science, I’ll waltz with you for a bit.
First, let’s see . . . planetary “epicycles’—as scientifically formalized by Ptolemy—were very accurately measured up until the time of Kepler. So, this indeed qualified as “data” per your/Grok’s assertion. Was it accurate data describing a physical epicycle? No, because there are no such things as planetary epicycles.
Next, there is this story from Richard Feynman recited in his commencement speech at Caltech in 1974:
“We have learned a lot from experience about how to handle some of the ways we fool ourselves. One example: Millikan measured the charge on an electron by an experiment with falling oil drops and got an answer which we now know not to be quite right. It’s a little bit off, because he had the incorrect value for the viscosity of air. It’s interesting to look at the history of measurements of the charge of the electron, after Millikan. If you plot them as a function of time, you find that one is a little bigger than Millikan’s, and the next one’s a little bit bigger than that, and the next one’s a little bit bigger than that, until finally they settle down to a number which is higher.
“Why didn’t they discover that the new number was higher right away? It’s a thing that scientists are ashamed of—this history—because it’s apparent that people did things like this: When they got a number that was too high above Millikan’s, they thought something must be wrong—and they would look for and find a reason why something might be wrong. When they got a number closer to Millikan’s value they didn’t look so hard. And so so they eliminated the numbers that were too far off, and did other things like that. We’ve learned those tricks nowadays, and now we don’t have that kind of a disease.”
I’ve given reasons why the “air” in bubbles trapped in ice cores may not be representative of atmospheric air at the time those bubbles were sealed by surrounding ice. Accurately measuring their compositions today does not convey any degree of accuracy for them representing reality at the time they formed.
Thanks for the opportunity to dance a bit.
Good observation.
Portraying them as anything more than local results is expanding their use beyond what is being measured.
Why don’t we just use a single thermometer at the same location to judge the change in global temperature?
Or better yet as an indicator of global *CLIMATE* change.
Because temperature differs extremely from place to place.
CO2 differs very little in 95% of the atmosphere.
More than 95% of Earth’s atmosphere exists away from the Law Dome ice coring location.
Yes, Law Dome is not a good proxy for Point Barrow or even MLO because of the differences in the seasonal variance.
Agreed. If you are interested in the seasonal variations, you have to use the data (CO2 and 13C/12C ratio) from each observatory. I recommend viewing the video provided by NOAA at https://gml.noaa.gov/ccgg/trends/history.html
If you are interested in inter-annual changes, it is best to use the same data, but with the annual cycle removed (e.g. as published by Scripps). This is essential if using Keeling plots (not to be confused with the Keeling curve) to investigate ENSO-caused variations.
If you are only interested in longer term trends then the Law Dome data is a surprisingly good proxy (as demonstrated by the overlap with observatory data).
Agreed. If you are interested in the seasonal variations, you have to use the data (CO2 and 13C/12C ratio) from each observatory. I would also recommend viewing the video provided by NOAA at https://gml.noaa.gov/ccgg/trends/history.html
If you are interested in inter-annual changes, it is best to use the same data, but with the annual cycle removed (e.g. as published by Scripps). This is essential if using Keeling plots (not to be confused with the Keeling curve) to investigate ENSO-caused variations.
If you are only interested in longer term trends then the Law Dome data is a surprisingly good proxy (as demonstrated by the overlap with observatory data).
Ice cores at best give CO2 average levels over less than a decade.
The difference between Barrow and South Pole for yearly averages currently is 5 ppmv, while humans emit 5 ppmv/year for 90% in the NH…
Each annual average you add to a difference trend increases the measurement uncertainty. The uncertainties ADD. You have yet to specify what the measurement uncertainties are for the measurements, nor are you propagating the uncertainties into long term differences.
Your figures are meaningless without the measurement uncertainties being part of an uncertainty budget and being properly propagated.
So what? As we are interested in the trends of the past, not what happens within one year or even within 10 years…
The yearly averaged differences today differ some 5 ppmv between Barrow, near the North Pole and measured at the South Pole.
That is while human emissions are for 90% in the NH and it takes time to pass the ITCZ, which allows only 10% air passing between the NH and SH.
The change in CO2/year in the atmosphere currently is about 2.5 ppmv/year, thus the South Pole measurements lag Barrow only with two years delay.
The “fastest” huge changes in the past were 100 ppmv between a glacial and interglacial period: over a period of some 5000 years, or 0.02 ppmv/year. I don’t think that the levels at Barrow and the South Pole were that different in those times…
You admitted earlier that CO2 is not well-mixed near the surface, only at altitude.
Only not well mixed over land, up to a few hundred meters height, not over the oceans, where there are no problems…
Thus in maximum 5% of the atmosphere by weight.
If different ice cores with extreme differences in temperature and snow accumulation and a direct overlap of 20 years with atmospheric measurements are not sufficient to show that the ice core measurements – at least for CO2 – are accurate enough for knowing past levels within 5 ppmv, then what is for you sufficient?
CO2 measurements by chemical methods?
Stomata data proxies?
Nothing?
IMHO, science currently has NO MEANS of determining atmospheric concentrations of CO2 prior to about 1850 to an accuracy of +/- 5 ppmv, either as a global average or at a specific geographic location.
Among other things, I note that the average CO2 in 1850 is stated to be around 280 ppmv, so a measurement to +/- 5ppmv would be equivalent to a measurement accuracy of better than +/- 2% in the face of MANY complicating uncertainties.
I invite anyone to prove me wrong.
“accurate enough”
This is totally “unscientific” statement. It does not specify what the measurement uncertainty interval is nor does it establish a level at which the uncertainty interval is “accurate enough”.
“knowing past levels within 5 ppmv, then what is for you sufficient?”
Sorry, but you are mixing different things together that have no connection at all…
“5 ppmv is more than accurate enough to detect a change of 100 ppmv over a period of 5000 years”
Here we go again: “more than accurate” is *NOT* scientific at all. It is magic thinking and handwaving.
Exactly *what* was the measurement uncertainty of a measurement made 5000 years ago? And exactly what is it a measurement of?
From JCGM 100-2008; “3.1.2 In general, the result of a measurement (B.2.11) is only an approximation or estimate (C.2.26) of
the value of the measurand and thus is complete only when accompanied by a statement of the uncertainty
(B.2.18) of that estimate.”
So what? Since these mixing problems *are* part of the assumed “average” value just how is the mixing problem adjusted for? And if vegetation is a factor then how is the 30% greening of the earth over the past 40 years or so handled since it would extend the variance of the land based data?
“What do you think was the difference for a change of 0.02 ppmv/year 800,000 years ago?”
How can that be determined if one doesn’t have a full description of the measurements and their measurement uncertainties? You and climate science just ignore that problem making thus making your “calculation” meaningless.
It was Anthony Watts in his addendum to this article who states, “Grok does quite well with scientific questions.” I simply utilized the same tool. Your suggestion of using discretion in believing Grok or any other AI tool might be legitimate and, if so, casts doubt about Anthony’s use of Grok to try and validate Marohasy’s claims in the article.
Well said!
Grok is wrong again. A distinction should be made between an instrumental measurement of something that represents its current state and something that was emplaced long ago and has had an opportunity to be changed by diffusion, dilution, or melting of the encasing ice.
That is, the ice core measurements are not direct measurements of the composition of the atmosphere from the past, but are measurements of preserved samples that are assumed to be identical to what the atmosphere was x years ago. In that sense, the samples are proxies for the past atmosphere, which is no longer available for measurement.
Nick,
They become proxies the second the resulting measurements are portrayed as indicative of more than local conditions.
Complete nonsense, else every thermomete measurement, every gas analysis, salinity analysis, water purity etc is a proxy. Not to mention mining assays.
That is *EXACTLY* what they are.
You think a mining assay for copper deposits near Leadville, CO can be applied to a location just 20 miles downslope? It’s not even a proxy! It is a local measurement and can’t be applied to other localities.
Temperature and CO2 are no different. Neither temperature or CO2 is a “global” measurement. Assuming the temperature in Las Vegas tells you anything about the climate in Miami is just idiotic. Yet climate science believes it does or it wouldn’t try to use some kind of “average” temperature including those two locations tells you something about the global *climate*.
So, the overlap period of “excellent agreement” is what, at most 200 years?
And you previously posted a chart showing “data” from Law Dome samples going back to 1000 AD. That would be, ummmm, yeah, about 1000 years ago.
ROTFL.
(I hope this works!)
“Temperatures and atmospheric concentrations of carbon dioxide over the past 66 million years. Bottom numbers indicate millions of years in the past; right-hand numbers, carbon dioxide in parts per million. Hotter colors indicate distinct periods of higher temperatures; deeper blues, lower ones. The solid zigzagging line charts contemporaneous carbon dioxide levels; shaded area around it reflects uncertainty in the curve. (Adapted from CenCO2PIP, Science 2023)”
From here.
https://news.climate.columbia.edu/2023/12/07/a-new-66-million-year-history-of-carbon-dioxide-offers-little-comfort-for-today/
(Who knew the first coal-fired power plant dates back millions of years! (or maybe it was Doc Brown and his DeLorean?))
Unfortunately for the authors of the Columbia article, there is no evidence that CO2 had any bearing on temperatures during the Cenozoic. But disaster springs eternal in the alarmist mindset.
See this:
https://wattsupwiththat.com/2020/09/15/cooling-the-hothouse/
And this:
https://www.youtube.com/watch?v=pj-Iu1i317E
Spoiler alert, it’s all plate tectonics (mya) and orbital mechanics (kya).
Nick had put up a hockey stick type graphic for CO2.
I found that graph that is hardly a hockey stick for CO2 or temps.
(And it doesn’t show which came first, rising CO2 or rising temps.)
I love the sight of graphs in the morning.
Mauna Loa and Law Dome were collecting samples 1000 years ago.
Talk about gray beards!
Law dome was.
We had sensitive instruments 1000 years ago?
We had science stations on Antarctica in 1025?
We have the samples.
The second figure in the above article, labeled “Thermal effects”, and the paragraph stating:
“Next, there’s the chemistry. In seawater, CO₂ exists in equilibrium with carbonic acid (H₂CO₃), bicarbonate (HCO₃⁻), and carbonate (CO₃²⁻). The conversion of dissolved CO₂ to these species (and back) involves hydration/dehydration reactions, which can also exhibit a kinetic isotope effect.”, are highly misleading because they don’t mention the effects of:
— the oceans’ average pH being in the basic range (about 8.1, see https://www.noaa.gov/education/resource-collections/ocean-coasts/ocean-acidification ),
— the ocean saltwater being highly buffered to remain around this level, and
— CO2 concentrations (as a dissolved molecular gas) being driven to extremely low level as a direct result of this basic pH level, thus not at all delivering the partial pressure that would be associated with water of ph 7, or water in the acidic range (which is typical of “soda pop”, mentioned at the beginning of the article).
Refer to discussions of the Bjerrum plot for ocean water at https://en.wikipedia.org/wiki/Bjerrum_plot and, more highly recommended, the paper at https://www.soest.hawaii.edu/oceanography/faculty/zeebe_files/Publications/ZeebeWolfEnclp07.pdf
Despite my repeated and best attempts, WorldPress insists on reformatting the soest.hawaii.edu link I gave at the very end of my above post by adding at the end the characters “ ” Clicking on the link as reformatted by WorldPress results a 404/”not found” error.
Try copying the URL up to and including the “.pdf” end—that is, trim off those last six characters— and paste that directly into a web browser as a URL address and you should immediately see the full PDF version of the recommended paper.
Very interesting, as us biologists have been interested for a long, long, long time about such surfaces. That includes bubbles as in foam lines, Langmuir circulation, burping cetaceans, etc. One reason is that there is so much more oxygen in the atmosphere than in the water, especially salt, that lots of critters try with varying degrees of success to exploit it. Another reason is the very difficult measurement of gas transfer as an indication of the autotrophy of photosynthesis and hetereotrophy of almost everything pumping out carbon dioxide. Apparently we still don’t know much about it. Put a dome over the water which actually has been tried on a small scale. The ‘crisis’ that you don’t hear much about is the alleged decrease of ocean oxygen.
Rahlff, J. C., et al. 2019. Oxygen profiles across the sea-surface microlayer—Effects of diffusion and biological activity. Front. Mar. Sci. 6(11):1-14. https://doi.org/10.3389/fmars.2019.00011
I did a back of envelope calculation some years ago, on CO2 concentrations in ocean surface and atmosphere. Nothing to do with 13C and 12C, Nothing to do with the ‘greenhouse’ effect. Just total quantities of CO2. Each year, we humans added a known x tons of CO2 to the atmosphere. Without that x tons, a warming ocean would have added an estimated y tons. But because the x tons changed the difference in CO2 partial pressure between atmosphere and ocean, the ocean actually absorbed more CO2. So the actual increase in atmospheric CO2 was x/2, and if humans hadn’t added the x tons the increase would have been y. The proportion of the observed atmospheric CO2 increase due to mankind is therefore (x/2 – y) / (x/2) which is 1 – 2y/x, and the proportion due to ocean warming is 2y/x.
Just what those proportions are depends on y, and on there not being other major factors which I missed. From memory, 2y/x came out at about 10%, ie. about 10% of the observed CO2 increase is natural, but there is considerable uncertainty about the value of y.
My calcs also worked on the observed atmospheric CO2 levels over the years to find how long ‘excess’ CO2 stayed in the atmosphere. Again from memory, it came out as a half life of about 12 years, ie, the ‘excess’ would halve every 12 years. That is I think a much faster absorption of ‘excess’ CO2 than allowed for by the IPCC, or certainly than allowed for by climate activists.
Where Ferdinand Engelbeen and others go wrong IMHO is that they don’t have those y tons in their equations.
I haven’t asked Grok what it ‘thinks’.
We did the calculation and indeed, the warming of the oceans is good for 10% of the CO2 increase, 90% is man-made. Thus the bulk of the increase is man-made, that was the purpose of our article.
The calculated adjustment time is around 50 years based on the extra CO2 pressure in the atmosphere above the equilibrium (including the temperature influence) and the observed removal rate of CO2 out of the atmosphere:
A. is the increase in the atmosphere from human emissions, the observed increase and the influence of temperature on pCO2 of the oceans. The real CO2 pressure difference between observed and oceans also is plotted,
B. is the observed net sink rate of CO2 in nature.
C. is the calculated adjustment time, based on the polynomials to avoid too much noise…
warming of the oceans is good for 10% of the CO2 increase, 90% is man-made
Correction, 90% is other. Some of it is anthropogenic, certainly, but there no proof it is 100% man-made.
If man-made CO2 is 200% of the measured 100% CO2 increase, then besides the 10% that warming ocean surfaces would introduce anyway, the 90% is certainly man-made. Not the initial fossil fuel molecules, but the increase in total mass, as the main other possible sources are turned into net sinks…
“Where Ferdinand Engelbeen and others go wrong IMHO is that they don’t have those y tons in their equations.”
The calculation seems right. But the conclusion is wrong. The y is in response to warming – ie AGW. It is a feedback, and also caused by burning carbon.
With China, India going guns over COAL fired power stations, many third world countries finally throwing off the anti-CO2 shackles, and the USA now intending to increase coal usage…
.. there will be PLENTY of CO2 in the atmosphere for a long time to come.
Plant life will love it.
And there is nothing the climate stall-warts can do about it 🙂
Alright, GROK (which very well might be wrong here, it does no know truth from error, but it can summarize massive amounts of written text fairly well) says:
“carbon dioxide with carbon-12 outgasses into the atmosphere faster than carbon dioxide with carbon-13 at the ocean surface.”
Jennifer Marohasy, on the other hand, says: “…the ocean’s surface, warmed by the sun, fizzes CO₂ richer in ¹²C than the deep oceans 0‰?”
So, GROK agrees with Marohasy’s hypothesis — warming ocean near-surface waters will outgas 12CO2 faster than the heavier 13CO2. .
GROK’s agreement doesn’t mean it is necessarily true.
It could be tested fair simply by actual experiement — capturing ocean outgassing CO2 over in situ and testing it for 13CO2.
Which experiments were done many years ago: Jennifer and Grok are right…
However Jennifer and Ivan are wrong on where it happens and the direction of the CO2 flux:
The main shift in isotopic composition is not in the the calcification: the δ13C of the carbonate of sponges, corals, coccoliths,… does hardly differ from the δ13C of the surrounding waters.
The main shift is at the water-air border (and back): – 10 per mil from water to air and -2 per mil in reverse. Giving – 8 per mil for equal ins and outs.
As the ocean surface is between +1 and +5 per mil, the atmosphere was around -6.4 +/- 0.4 per mil over the past 800,000 years, despite huge changes in vegetation over that period. The ocean surface was dominant.
Until around 1850: then there is a drop of -2 per mil in exact ratio to fossil emissions (at around -25 per mil)…
Moreover the net CO2 flux is proven from the atmosphere into the oceans, not reverse…
The North Atlantic (AMO) certainly absorbs less CO2 when in its warm phase, which a very convenient feedback for regions where drought increases during a warm AMO.
Seriously, who cares?
Adding CO2 to the atmosphere stops a little more infrared reaching the surface.
Result? Reduced daytime maxima, nighttime minima don’t drop as far.
Much ado about less than nothing.
Question to Brave AI: The preferential precipitation of light fraction abiotic ooid mineral carbonates in the desert beach swash zone results in the release to the atmosphere of carbon dioxide gas from bicarbonate ion dissociation. Does this released carbon dioxide gas also have a light carbon fraction?
Brave AI Answer (AI inputted caps): Yes, the carbon dioxide (CO₂) gas released from the dissociation of bicarbonate ions (HCO₃⁻) during the precipitation of abiotic ooid mineral carbonates in the desert beach swash zone will also have a lighter carbon fraction. This is due to the same kinetic isotope effects that favour the precipitation of lighter carbon isotopes (¹²C) over heavier isotopes (¹³C).
Mechanism of Isotope Fractionation
Chemical Equations
The process can be described by the following chemical equations:
Isotope Fractionation
Summary
Thus, the CO₂ gas released to the atmosphere from the dissociation of bicarbonate ions in the desert beach swash zone will indeed have a lighter carbon fraction (¹²C).
Now isn’t that an interesting answer?
Postscript: In addition to the natural release of light fraction CO2 gas into the atmosphere from carbonate beach sand abiotic ooid grain formation, there is also the issue of the more extensive marine precipitation process of whitings.
Yao, Y., Hu, C. and Barnes, B.B., 2023. Mysterious increases of whiting events in the Bahama Banks. Remote Sensing of Environment, 285, p.113389. https://www.sciencedirect.com/science/article/abs/pii/S0034425722004953
Interesting and quite accurate…
Some remarks: there is a difference between mineralization into solid carbonates by evaporation of water and the biological build-up of carbonates by living creatures.
The precipitation of carbonates gives an increase in δ13C of the remaining CO2, while the build-up by biological processes is near neutral in δ13C. Thus leaving the same δ13C level in the remaining CO2, thus lower than by evaporation.
It is the next step that makes the main drop in δ13C: from solution in the surface water into the atmosphere that gives in average -8 per mil drop, compared to surface waters.
Despite that millions of years old mechanism, which maintained the atmosphere at around -6.4 per mil, that doesn’t explain the recent drop of -2 per mil δ13C since about 1850…
On the subject of ocean water emission of carbon dioxide gas there is this paper by Professor Harald Yndestad:
Yndestad, H. (2022) Lunar Forced Mauna Loa and Atlantic CO2 Variability. Science of Climate Change Vol. 2.3 pp 258-274.
Abstract:
The source of atmospheric CO2 variations is poorly understood. At Mauna Loa Hawaii, atmospheric CO2 has been recorded from 1959. This is a short period for a reliable variability signature identification. From the 19th century, atmospheric CO2 has been recorded in several short periods over the Atlantic Ocean and Europe. A number of these data series are compiled into a single atmospheric Atlantic CO2 data series from 1820 to 1960. Altogether, this time series covers atmospheric CO2 records over a total period of 200 years. In this investigation, a wavelet spectrum analysis identifies the signature of Mauna Loa atmospheric CO2 growth from 1960 to 2020 and Atlantic atmospheric CO2 for the period 1870 to 1960. The result reveals that the Atlantic CO2 variability from 1870-1960 coincides with Mauna Loa CO2 growth variability, global sea surface temperature variability and lunar nodal tide variability. The Atlantic CO2 signature and global sea surface temperature signature and the have a phase difference of p/2 (rad), which reveals a sea temperature driven atmospheric CO2 variation. The CO2 variability signature coincides with the global sea temperature signature and the lunar nodal signature spectrum. The identified lunar nodal tide spectrum reveals a chain of events from lunar nodal tide variations to global sea surface temperature variations and atmospheric CO2 variations. A lunar nodal tide spectrum in atmospheric CO2 growth reveals that CO2 is not controllable.
https://scienceofclimatechange.org/wp-content/uploads/Yndestad-2022-Lunar-Forced-CO2-Variability.pdf
Harald Yndestad: Alma Mater Norwegian University of Science and Technology (NTNU). Dr. philos Professor (Full) Faculty of Information Technology and Electrical Engineering at Norwegian University of Science and Technology
https://www.researchgate.net/profile/Harald-Yndestad
A short reply…
While there is an influence of the lunal tides, C.D. Keeling also noted that in the first decades of the measurements at Mauna Loa and these were in the order of 0.2 ppmv in variability around the trend.
Year by year variability indeed is mainly caused by temperature in the order of 3.5 ppmv/°C, but not caused by the ocean surface temperature changes, but by the much faster reaction of plant life on short living temperature changes. That can be deduced from the opposite δ13C and CO2 changes:
Further, the work of professor Yndestad heavily leans on the work of the late Ernst Beck. I have had a lot of discussions with Ernst about his work in the period 2000-2010 until his untimely death.
While he did an enormous work to dig out a lot of forgotten historical measurements, I did disagree with him on their relevance. Many of the old measurements were done in places completely unsuited for “background” CO2 measurements.
The main “peak” of 1941 was based on a long series of measurements at Giessen, mid-west Germany, which shows a stdev of 68 ppmv (1 sigma)… A modern station at a few km of the old station still has a stdev of over 20 ppmv, while the station at Mauna Loa shows a stdev of 7 ppmv, including a + and – 5 ppmv seasonal amplitude…
That all is reflected in my comment on Beck’s 2020 posthumously publicated work, also published by the SCC:
https://scienceofclimatechange.org/wp-content/uploads/Engelbeen-2023-Beck-Discussion.pdf
Did I miss the link to Jennifer’s blog?
If so here it is again:
https://jennifermarohasy.com/jenns-blog/
There is some error in the “thermal effect” figure: the “cooler” and “warmer” arrows must be reverse… As far as I know, warmer means more solubility for carbonates and more CO2 release and reverse for colder…
Because of the previous discussion with Philip Mulholland, there is a difference in δ13C discrimination between evaporation and biological calcification by different living organisms like coccolithophores (tiny algue with a carbonate skeleton), corals and coralline sponges.
From Böhm et al:
“These sponges precipitate aragonite very close to isotopic equilibrium with ambient sea water”
That means that there is no discrimination in the remaining CO2/DIC after calcification and thus a lot lower than the δ13C discrimination found from evaporation. Despite that, there was a near constant δ13C level with a small variability of -6.4 +/- 0.4 per mil over the past 800,000 years in ice cores atmospheric CO2. Only dropping with some 2.0 per mil after 1850 in exact ratio with fossil emissions.
There is no way that the recent drop in δ13C (and the recent CO2 rise) comes from the calcification in the oceans.
Ferdinand, you state above: “Only dropping with some 2.0 per mil after 1850 in exact ratio with fossil emissions.”
Please would you explain how you reached this conclusion? As you will be aware, Figure 1 in Kőhler et al (2006) (the bit you and your co-authors failed to show in your report for the CO2 Coalition, where you reproduced only one half of the published version and edited out the other half) demonstrated, by application of the Keeling plot to the Law Dome data, that the δ13C content of the incremental atmospheric CO2 was -13.1‰ (R squared of 96%) in stark contrast to the ratio for fossil fuels, which you give as -26‰. How do you determine this to be the “exact ratio”?
It is even possible to approximate this by comparing the scales on the Böhm et al (2002) plot (from which I calculate -12.9‰), which reflects the mass balance of 13CO2 (completely ignored in the above discussions).
Jim, there is an “apparent” constant supply of CO2 with a δ13C level of around -13‰.
Apparent, as there is no such huge source in nature at all.
There are only two important (possible) huge sources of low 13C: living organics (at around -24 per mil) and fossil organics (at average -25 per mil).
Living organics can be excluded, as the O2 balance shows that these are increasing all over the world, leaving +24 per mil δ13C behind. Thus remains only fossil organics at -25 per mil as possible bulk source.
Why is the δ13C drop in the atmosphere then not steeper? Because there is the pesky deep oceans, which return 1,000 year old waters with the isotopic composition of that time.
One can even calculate the size of that flux, assuming that after passing the water-air border, the δ13C level is at the pre-industrial -6.4 per mil level:
With a supply of around 40 PgC/year deep ocean return waters, you have your -13 per mil δ13C “mix”…
The discrepancy in the years before 1980 probably was from vegetation: more source than sink, after 1990 an increasing net sink (based on the O2 balance).
No, this is not an “apparent” constant supply of CO2 with a δ13C level of around -13‰. There is a real, measured, trend of increasing atmospheric CO2 with a NET δ13C content of around -13‰. Just like the CO2 data, the δ13C value is a net value: i.e. it incorporates all sources/sinks/fractionation etc. that affect the measured atmospheric value in a material way. You are mixing up data and models. Valid models may involve some or all of these issues, but they must match the data. As an example, let’s assume we have only CO2 measurements for Law Dome plus an initial δ13C value. I have a model that says that the incremental CO2 has a constant net δ13C level of exactly -13‰ from which I compute the future δ13C values (shown below as green diamonds). How would that compare with your model shown above?
This is a much better match, I would suggest. Of course, my model must match the data since the net δ13C value of the incremental CO2 is determined from the data using the Keeling plot, which shows a strong linear relationship reflective of a constant net δ13C value for the incremental CO2. It is why the issue of ‘constancy’ is both scientifically interesting and a fundamental requirement of any proposed model.
Your hypothetical model of a single source with a fixed δ13C content is obviously invalid, but this observation is not something that I have ever claimed, nor is it an absolute requirement of the Keeling plot (though it is a common assumption). Your failure to respect the observed data relationship is the reason your model does not match the observations very well.
It is beyond the scope of this comment to delve into application of Keeling plots to direct atmospheric measurements available since the late 1970s other than to note that the South Pole observatory data (with almost no seasonal cycle) shows an average net δ13C content of -13.0‰ and an R squared of 0.99 (figure below), essentially the same as the Law Dome data at -13.1‰.
Jim, there simply doesn’t exist a huge source of -13 per mil δ13C that makes that the atmosphere (and ocean surface) shows such an enormous drop of δ13C, not seen in 800,000 years. If you can show me such a source, we can have a better discussion about the real world.
Moreover, a “natural” source that exactly mimics human emissions at exactly the same time? And what happened with the -25 per mil δ13C fossil fuels?
We know the fossil emissions and their δ13C level and quantities since 1850 with reasonable accuracy. The plot I have made shows what happens with these emissions in the atmosphere: only about 1/3 remains there, the rest is redistributed into vegetation and the oceans.
The discrepancy in the years before 1980 was thought to be from vegetation: more source than sink in that period (land use changes?). In my plot vegetation did not change.
As I said above, I consider that the data do not support a model of “a single source with a fixed δ13C content”. So which of these two criteria may be invalid? Given the long term ‘constancy’, any combination of sources and/or sinks where one of them varies significantly in rate over time is very unlikely to be supportable. However, I also maintain that you cannot ignore the data that so clearly demonstrate such a ‘constancy’ without providing any evidence that it is invalid. In fact, the relationship is so strong that it can be used to predict future atmospheric δ13C values based on CO2 alone (I am sure that you have seen the way it can be used to show why the initial model of Keeling et al (2017) was wrong but, if not, let me know if you are interested).
Several years ago, I discovered that a possible reason for incremental atmospheric CO2 having an average of -13‰ was that it was fluctuating around two ‘extremes’ as a direct result of the El Niño-Southern Oscillation (ENSO). ENSO is not only the dominant driver of inter-annual global temperature fluctuations, it is also a key driver of such changes in the atmospheric CO2 growth rate. Significant El Niño events lead to an increased atmospheric CO2 growth rate, while La Niña events lead to lower CO2 growth rates; this is not controversial, as far as I am aware.
My early analyses suggested that the net δ13C content had also changed, with significant El Niño events leading to a lower δ13C value of the incremental CO2 (below -13‰) and La Niña events leading to higher values, the latter probably being due to enhanced ocean upwelling and supported by short periods of parallel changes of increasing atmospheric CO2 with increasing atmospheric δ13C. Tans (2020) in the paper “Reminiscing on the use and abuse of 14C and 13C in atmospheric CO2” states: “Isotopic exchange is large enough sometimes to have the d(δ13C)/dt growth rate go in the “wrong” direction [i.e. to increase], whereas the dCa/dt [atmospheric CO2] growth rate is always positive” which he speculates could be due to a ‘contribution’ from the oceans.
I created a simple set of models to test this hypothesis. First:
In Figure 1, I show the actual CO2 and δ13C values (seasonal cycle removed by Scripps) associated with the El Niño of 1997-1998, followed by the double La Niña of 1998-1999 and 1999-2000. It is clear that the CO2 growth rate increases significantly in late 1997 and drops back to ‘normal’ in late 1999 or thereabouts. It is also clear the δ13C values drop very rapidly starting at the exact same time as the CO2 rate increases.
In Figure 2, I have superimposed (in green) calculated δ13C values based solely on the CO2 data, but assuming a constant value of -13‰. This does show a slight decrease in δ13C due to the increased growth rate in the CO2, but nowhere near to matching the actual data.
Next:
In Figure 3, I adjust the model to use a value of -26‰ between late-1997 and mid-1998, and then revert to -13‰ thereafter. Finally, in Figure 4, I use 0‰ from mid-1998 to late-1999 and -13‰ thereafter. Please note that I am not suggesting these values are anything more than directionally indicative.
I have just started to revisit my hypothesis and, with significantly increased data availability and quality, I am finding preliminary results over a much longer period that are supportive. I still need to prepare better quality figures so work is currently on-going. In any event, I believe that such variations in δ13C content may not be incorporated in current published models, which might explain the difficulty the ‘experts’ are still having with reproducing the inter-annual changes.
Jim, a similar ratio happens with the amount of CO2 in the atmosphere: about 50% of human emissions remain (as mass) in the atmosphere. In so far that the IPCC gets accused of assuming that it will be always the case and thus that nature discriminates between “natural” and “human” CO2, which was never said or implied by them.
What happens in reality? Human emissions increased over time in near exact linear way, with hardly any variability, but a near straight line increasing from near zero to some 10 PgC/year nowadays.
The net result: a slightly quadratic increase in the atmosphere above the equilibrium for the current average SST, with as result a slightly quadratic increase in net sink rate (somewhere in nature) and thus an apparent “fixed” ratio between human emissions and net sink rate of around 50%. Of course that is not “fixed” at all, as if human emissions would halve and stay fixed on the current net sink rate, the increase in the atmosphere would be zero and thus a “fixed” ratio of zero between increase in the atmosphere and human emissions.
That is also the cause for the δ13C ratio: because of an increasing low-13C supply from fossil fuels and a fixed response from other CO2 sources with a higher (oceans) or similar (vegetation) δ13C level, about 1/3 of fossil fuel CO2 still is in the atmosphere, 2/3 is already redistributed in oceans and vegetation…
Again, there doesn’t exist another low-13C source than recent organics and fossil organics and the former is a net absorber of CO2 and preferential 12CO2. thus leaving +24 per mil δ13C behind in the atmosphere…
The opposite changes of CO2 and δ13C in short time over the 1998 El Niño and subsequent La Niña’s show that vegetation is the main response to temperature variations on short periods (+3.5 ppmv/K), opposite to the seasonal changes (-5 ppmv/K), see the graph at:
https://wattsupwiththat.com/2025/04/10/whose-co%e2%82%82-is-it-anyway-ocean-fizz-or-smokestack-blame/#comment-4060166
Over very long periods, the oceans are dominant, because there were hardly any δ13C changes over the past 800,000 years, until humans were starting to use fossil fuels in linear rate, each year more.
But if you find a new source, that exactly mimics the human addition of low-13C CO2, let us know and also what then happened with the -25 per mil human supply of CO2…
Ferdinand,
Part 1
.
The short answer to your question is perhaps ‘phytoplankton’ with a h/t to Tom Quirk who published similar views to what follows some years ago. I cannot find the original paper (published at or linked from Jo Nova’s site, which seems to be down at present), but I believe this may be a link to the original article:
https://iowaclimate.org/2019/06/01/new-finding-phytoplankton-are-much-bigger-players-in-co2-levels-than-realized/. I see that he has published a number of papers on related issues and is a member of the CO2 Coalition, so you may well be aware of his work.
My position is that there are two primary and distinct processes in play. First, anthropogenic CO2 emissions are dwarfed by natural seasonal, inter-annual and longer term atmospheric variations. On release to the atmosphere, they immediately become part of, and indistinguishable from, the diurnal CO2 cycle which is largely driven by photosynthesis/respiration of the terrestrial biosphere. We see their addition to the CO2 cycle by the increasing size of the annual (seasonal) cycle in the atmosphere and can conclude that it must be largely driven by terrestrial effects of the northern hemisphere because of the cycle’s much smaller extent in the southern hemisphere and is virtual non-existence at the South Pole (https://www.scrippsco2.ucsd.edu/graphics_gallery/other_stations/index.html).
The second process is global in nature, likely reflecting the extent of the oceans, especially in the southern hemisphere. Both trends are clearly visible and identifiable on a Keeling plot for Mauna Loa:
The intercepts given by the red and green lines approximate the δ13C trend of the two processes: – 26‰ for the two-way seasonal cycle and -13‰ for the one-way increasing CO2 trend seen globally (i.e. at all observatories). As proof of this distinction, the Keeling plot for the South Pole shows only the latter trend:
Note that the data shown have had the seasonal cycle removed (by Scripps) but this has a negligible effect. The linear fit shows an intercept of -13.0‰ and r-squared of 0.99.
The dominant driver of inter-annual changes in atmospheric CO2 growth rate is related to fluctuations in the El Niño-Southern Oscillation (ENSO) of the tropical Pacific Ocean. The major changes in rate of growth (e.g. for the 1997-1998 El Niño) show virtually no timing differences between Mauna Loa and the South Pole, consistent with a source in the tropics, but with global reach (i.e. it affects both hemispheres simultaneously and to a roughly equal extent):
In my view, your explanation of the response to the 1997-1998 El Niño and subsequent La Niña events is inconsistent with the data. Look again at the simple models. Atmospheric CO2 is growing throughout the model period (Figure 1). The average seasonal cycle is excluded (by Scripps). This is the situation mentioned by Pieter Tans: atmospheric δ13C is increasing at the same time as atmospheric CO2 is increasing. This means that the incremental CO2 must have a net δ13C higher than the atmospheric value.
This interpretation is also clearly demonstrated by the plot you linked to. Around the year 2000, for example, your plot shows that the rate of change of δ13C goes positive at the same time as the rate of change of atmospheric CO2 is positive. This evidence strongly supports some oceanic input to the increasing CO2. La Niña events reflect periods of upwelling of colder waters; these would be expected to have a higher δ13C content, which is what my simple model analyses show. Conversely, a very strong El Niño (e.g. 1997-1998) virtually shuts off the upwelling and, inevitably, we observe a lower δ13C content for the increased CO2 growth, not least because we know that the average remains at the long term constant level of -13‰, as unequivocally demonstrated by the Keeling plots.
In addition, and crucially, the 1997-1998 El Niño led to a huge ‘die-off’ of phytoplankton. It would be reasonable to assume that this would lead to a significant release of CO2 from the oceans due to an excess of near surface CO2 combined with the warmer waters of the El Niño. Finding a consensus in the literature on the effect of phytoplankton die-off is very difficult with a lot of relevant aspects ‘requiring further research’.
Part 2
However, based on Young et al (2013), there is evidence from POC data that photosynthesis of phytoplankton reflects significant fractionation reducing the δ13C(CO2) of around -8‰ (surface waters) to a δ13C(POC) of about -23‰ (collected at depth), i.e. discrimination of about -15‰. These latter values are similar to those mentioned by Philip for δ13C(POM) values in the Indian Ocean. Finally, according to Keeling et al (2017), marine photosynthetic discrimination is -13.5‰ so one might reasonably assume that these low δ13C values would also be reflected in the CO2 associated with the phytoplankton die-off, presumably subject to further fractionation at the sea-air interface.
In summary, I agree with you that the cause of the lower δ13C content could indeed be ‘vegetation’, but perhaps it is ‘oceanic vegetation’ in the form of phytoplankton.
Ferdinand Engelbeen: Thank you for your comments. My contribution to this discussion is based on my understanding of carbonate sedimentary geology, gleaned from expert tutelage that I received when visiting the Caicos Carbonate platform in the summer of 1991 (see my WUWT post http://wattsupwiththat.com/2013/10/20/the-oceanic-central-heating-effect/
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You say “As far as I know, warmer means more solubility for carbonates”, this statement of yours is incorrect because it does not apply in all environmental circumstances for the following reason: The science of mineralogy has established that a given crystal is stable in its environment of formation, but when translated to a different environment it becomes unstable. In the case of carbonates these minerals are precipitates that form in saturated marine water and are stable there, but when removed from the sea by uplift and exposed to a warm humid acidic sub-aerial environment (for example) then the carbonate minerals become unstable and leach away. It may seem paradoxical but in their environment of formation carbonate minerals become less soluble as the temperature of the water increases.
For the specific case of calcium carbonate this is because in the marine environment the dissolved calcium is a divalent ion whereas bicarbonate is a monovalent ion, however carbonate is a divalent ion. Therefore, in the process of generating calcium carbonate (CaCO3) precipitate from ionic solution, molecular carbon dioxide gas is also formed and released. This is because two bicarbonate ions are involved in the precipitation reaction. As the temperature of the marine water rises there is less carbon dioxide gas in the water body. Therefore, the solid calcium carbonate precipitate cannot react back to soluble calcium bicarbonate and so the calcium carbonate becomes more insoluble as temperature increases and not less.
Thanks Philip for your reply. I was aware of parts of that story, but in the case of many carbonate deposits, the reaction is not by the simple ionic deposit of solid carbonates out of bicarbonates, but by living creatures, that use a lot of energy to get Ca++ and 2x HCO3- together in their body to form the CaCO3 shells + CO2 + H2O.
Most deposits in the past were formed that way by the grandparents of the current species (mostly by coccolithophores).
The difference is reflected in the δ13C level, which is near-neutral compared to the sea surface DIC δ13C level. One particular deposit, Pee Dee Belemnite, therefore was chosen as standard for δ13C levels.
If carbonates are formed by simple chemical reaction (maybe in the Dead Sea or similar), the δ13C level of the deposit would be a lot lower (according to Grok…).
As far as I know, in the open oceans of today, there is neither a chemical deposit of carbonates, nor a spontaneous dissolving (or we would miss all the beautiful corals…), at least not in the upper ocean depths. All carbonates in open oceans are created by living organisms… But I can be wrong.
The main problem with the arrows is in the other end: higher temperatures surely release more CO2 and colder oceans absorb more CO2, thus the arrows for that part are certainly wrong.
Moreover, Feely et al measured some average 7 μatm higher pCO2 in the atmosphere than in the average ocean seawater:
https://www.pmel.noaa.gov/pubs/outstand/feel2331/exchange.shtml
Thus the net CO2 flux is from the atmosphere into the oceans, despite warmer oceans and calcification reactions…
Thanks Ferdinand. My focus is and remains on the abiotic part of the story. In the current Holocene the abiotic part of the carbonate formation process is believed to be about 10% of the gross carbonate sedimentation. From my personal experience of visiting West Caicos Island in June 1991 the process of ooid carbonate sand grain formation in this carbonate platform environment is continuous and ongoing. Under the active force of the Trade Winds the newly formed abiotic ooid sand grains saltate across the beach from the swash zone at the water’s edge and accumulate above storm level as actively accreting aeolian carbonate sand dunes.
tinyurl.com/GoogleMap-WestCaicos-EastBeach
The key point about abiotic carbonate sedimentation is that there is no cell membrane capture of the released carbon dioxide gas and therefore this warm water light fraction gas goes directly into the atmosphere from the swash zone.
Shallow sea water temperatures in the Caribbean in high summer can exceed 30 Celsius e.g Nueva Gerona, Cuba. Afternoon water temperatures in the carbonate beach swash zone typically exceed those of the open water setting and therefore the process of carbonate light fraction dissociation will favour C12 emission into the atmosphere. In this context it is worth noting that the carbon isotope ratio of the solid ooids is not equivalent to that of the formed and released gas because two separate and distinct bicarbonate anions are involved. One bicarbonate anion forms the calcium carbonate precipitate and the second anion dissociates in the water to form the carbon dioxide gas. These are clearly two separate decomposition reactions with distinct temperate dependent isotope fractionation effects.
Ferdinand: You state “As far as I know, in the open oceans of today, there is neither a chemical deposit of carbonates, — at least not in the upper ocean depths”
I invite you to research the topic of Whitings – the process of shallow water precipitation of calcium carbonate (Aragonite) in the shallow marine waters of the Bahamian Banks.
The formation of whitings on the Little Bahama Bank.
Thanks Philip for the link…
If I have understand it properly, the whitening is mainly at high temperatures and shallow waters. When temperatures drop, that should go back into solution, if the theory from Jennifer and Ivan was right, giving at least a large part of the seasonal changes and moreover from the current CO2 increase in the atmosphere.
The problems with that theory are manifold:
Thus the theory is already refuted by known facts, before it is even worked out…
Thanks, Ferdinand, for your reply. Your introduction of oxygen into the discussion is interesting, so I will follow your lead and move to a discussion of the big picture open ocean setting. I note that you always mention DIC (Dissolved Inorganic Carbon) however when considering the organic generation of oxygen, I suggest that POM (Particulate Organic Matter) is the more appropriate data to study.
The following paper for Tropical Indian Ocean Particulate Organic Matter gives a δ13C range of -21.4 0/00-to -26.82 0/00 (i.e. 13C 10.8771 0/00 to 13C 10.8175 0/00). These δ13C values interestingly lie in the same 13C depletion range as Coal which has a δ13C range of -24.80/00-to -28.30/00 (i.e. 13C 10.8397 0/00 to 13C 10.8012 0/00).
Given that we can expect that the Tropical Indian Ocean is an area of biogenically derived Carbon Dioxide formation, then the POM data demonstrate that the tropical ocean water organic biosphere functions with depleted 13C values.
Soares, M.A. et al. 2015. Latitudinal δ13C and δ15N variations in particulate organic matter (POM) in surface waters from the Indian ocean sector of Southern Ocean and the Tropical Indian Ocean in 2012. Deep Sea Research Part II: Topical Studies in Oceanography Vol. 118 Part B pp186-196. https://www.sciencedirect.com/science/article/abs/pii/S0967064515002118
Indeed, POM is not mentioned, as the focus was on the inorganic carbonate deposits.
If one looks at the whole food chain in the ocean surface, the net δ13C gets between +1 and +5 per mil δ13C in the surface waters, depending of how much organic carbon drops out of the food chain into the deep oceans, where it is re-mineralized to CO2 are gets natural gas or oil, if you have the time to wait…
The shells that were build by different organisms where δ13C-neutral and reflect the δ13C of the surrounding waters. At least for coccolithophores and coralline sponges. I don’t know of the discrimination in coral carbonates…
If the deposits were from pure inorganic reactions, that would give a much higher δ13C in the deposits, but I have not seen anything in that direction…
Ferdinand: You state “The main problem with the arrows is in the other end: higher temperatures surely release more CO2 and colder oceans absorb more CO2, thus the arrows for that part are certainly wrong.”
Here is the source of the figure that Jennifer has in her presentation:
Figure 2. Variations in thermodynamic constants with temperature are proposed to favor precipitation of CaCO3 in summer with pH falling, coupled with absorption of CO2 from the atmosphere from spring. In autumn and winter, the process is reversed, dissolving calcite (x moles) and releasing CO2 to air (y moles), with calcite dissolution in colder water exceeding CO2 emissions (x > y).
Kennedy, I.R., Runcie, J.W., Zhang, S. and Ritchie, R.J. 2022 A New Look at Physico-Chemical Causes of Changing Climate: Is the Seasonal Variation in Seawater Temperature a Significant Factor in Establishing the Partial Pressure of Carbon Dioxide in the Earth’s Atmosphere? MDPI (Multidisciplinary Digital Publishing Institute) Thermo 2022, 2(4), 401-434; https://www.mdpi.com/2673-7264/2/4/28