Frans Schrijver
Klimaatfeiten.nl (in Dutch)
Apr 15, 2022
The general view in society is that human emissions of CO₂ are the all-determining cause of the increased concentration in the atmosphere. Most scientists and even many climate skeptics do not question this. There is some debate about how long this extra CO₂ will stay in the atmosphere, but that’s about it. That’s remarkable, as several scientists have published extensively on the flaws and inconsistencies of this narrative. By looking at the significant increase in the CO₂-flows from and to land and sea it’s in fact easy to see that the CO₂-rise is largely due to natural causes.
The idea that human CO₂ is the all-determining cause of the increased concentration is based on the assumption that the natural inflows and outflows are always and exactly in equilibrium with each other. Based on this perfect equilibrium thinking, human emissions, even though they are relatively small, cause a perturbation year after year. In the so-called global carbon budget[2] about 10 PgC of CO₂ is added every year, while the absorption flux has only increased by 6 PgC/yr (1 Petagram = 1 Gigaton = 1 billion tons). The concentration therefore continues to rise indefinitely as long as people emit CO₂.
To support this idea it is also assumed that human emissions accumulate in the atmosphere. Where you would expect a single residence time for a reservoir with in- and outflows, the IPCC-models calculate with a small residence time of about 4 years for natural CO₂ and a large one for human CO₂: “The removal of all the human-emitted CO2 from the atmosphere by natural processes will take a few hundred thousand years (high confidence)”.
Several scientists, including Murray Salby[9] and Hermann Harde[3], have published extensively on the flaws and inconsistencies of this narrative. They also showed that it is very illogical to think that a slight increase in the up-flux cannot be compensated by a larger down-flux. It’s like increasing the heat energy flow in a house by 5% and expecting that the temperature will keep on rising forever.
Despite this, belief in the IPCC’s model for the increase in concentration is persistent. In this article we will focus on one of the strangest assumptions: the idea that the in- and outflows are stable and in perfect equilibrium. Although they are about 20 times larger than anthropogenic fluxes and have different drivers for up and down, natural flows are not included in the material balance used in the models.
It is in fact easy to see that the increase in the CO₂ concentration is for the most part the result of natural changes, based on the following unmistakable observations.
- Fluxes to and from land and sea have increased significantly since 1750.
- The increase in these fluxes is natural, i.e. not due to human emissions.
- The growth of the natural fluxes can only take place at a higher concentration in the atmosphere.
- Natural fluxes have increased since 1750
The IPCC’s AR5 report[6] clearly shows that natural fluxes to and from land and sea have increased. We can see this in the well-known figure 6.1 from the AR5 report. In this figure (Figure 1) you can see that the total human emissions are almost 10 PgC/yr. The natural fluxes are much larger. To and from the sea this is about 80 PgC/yr, to and from land about 120 PgC/yr.
The fact that these natural flows have grown considerably since 1750 is visible in the figure from the color of the arrows. The black arrows indicate the original equilibrium situation as it once was in 1750. The red arrows indicate the new flows or the changes since that time. Emissions from the oceans have increased by 17.7 PgC/yr, emissions from land by 11.6 PgC/yr, so all together this amounts to almost 30 PgC/yr. The natural down fluxes have increased even slightly more.
If we show the important flows horizontally and in the correct proportion, the simplified picture looks like this (Figure 2).
It is now clear at a glance that natural emissions have increased by a factor of 3 more than human emissions. We also see that the natural absorption has increased, but less than is needed for balance. This leaves a net increase of about 4 PgC/yr towards the atmosphere.
- The increase in CO₂ flows is natural
The second question that has to be answered is what is the cause of this increase; is it a natural flux change or is it the result of human influence?
Oceans
Henry’s Law plays a central role in the inflows and outflows from the sea. This law says that the amount of dissolved gas in a liquid is directly proportional to the concentration of the gas. With a high CO₂ concentration in the air, water absorbs more CO₂; at a low concentration the absorption is lower. In addition, the ratio depends on the temperature. At a low temperature, water can contain a relatively large amount of CO₂; at a high temperature less (warm beer contains less carbonation than cold beer).
This means that temperature has a direct influence on the ocean’s emissions. A high temperature means more emission and less absorption, a low temperature exactly the opposite. We know that the global temperature has increased since 1750 by about 1 °C. The question is: how great is this influence?
Hermann Harde[5] has performed a calculation based on physical data. Using Henry’s Law, he calculated the change in partial CO₂ pressure with a temperature increase of 1 °C. From measurements it is known how much the outflow increases or decreases depending on the change in the partial pressure. At 1 °C temperature increase, this results in an increase in emissions from the oceans of 19 PgC/yr. This is in good agreement with the increase of 17.7 PgC/yr from the IPCC report of 2013.
It’s important to mention that this temperature sensitivity deviates from calculations that are based on ice core measurements in Antarctica. These data show a ratio of the order of 100 ppm at a temperature increase of 10 °C, so much smaller. However, it is highly questionable whether this ratio is correct. As early as 1978, Stauffer and Berner[12] concluded: “We estimate the fraction of CO₂, present in bubbles to be only about 20%. The remaining part is dissolved in the ice.” Other scientists such as Jaworowski[7] and Harde[4] have also discussed major imperfections of ice core measurements in various publications. Contrary to what is often assumed, the ice layers are not a closed system. The air in the air bubbles in the deep ice layers no longer has the same composition as when the air bubbles were formed.
The calculation of Harde is far more reliable as it is based on reproducible physical data and confirmed by the observed larger emission from the oceans. This greater emission leads to a higher concentration in the atmosphere and thus, under the influence of Henry’s Law, also to a greater absorption by the oceans.
Land
With respect to land emissions we have to distinguish between plant respiration and soil respiration. About half of the CO₂ that plants absorb through photosynthesis disappears almost immediately into the atmosphere in the form of plant respiration. The other half is converted into biomass (leaves, wood, roots, etc.) that ends up on or in the ground.
The study of Jae-Seok Lee (2011)[8] shows that the soil emission is strongly dependent on temperature. Lee’s graph (Figure 4) shows that there is an exponential relationship between soil temperature and emission. A 1 °C increase in soil with a temperature of 14 °C leads to 15% to 20% higher emissions.
A 2016 study by Zhang et al.[13] found that emissions in China from the soil had increased by an average of 28% over 50 years. If China is representative for the rest of the world, the increase in soil emissions is about 17 PgC/yr. This is greater but still comparable to the IPCC’s 11.6 PgC/yr.
The absorption of CO₂ on land has also increased. The world has become greener under the influence of the higher CO₂ concentration (Figure 5, left). According to NASA[14], the greening has resulted in an increase in plants and trees over an area equivalent to twice the size of the United States.
A 2017 study by Peng Li[11] has shown that the Net Primary Production (NPP) has grown by 11.8 PgC/yr since 1960 (Figure 5, right). The NPP is the amount of CO₂ converted to biomass by plants (during photosynthesis) minus the plant respiration. The growth of the NPP illustrates that the absorption on land has increased and confirms the aforementioned figures from the IPCC.
So also for land it is clear that temperature plays an important role in the rise of the CO₂ fluxes. The increase of the land fluxes is not related to human emissions, but can be well explained by the global warming of 1 °C. The absorption of CO₂ on land has increased as a result of the global greening, under the influence of the higher atmospheric CO₂-concentration.
- The growth of the natural fluxes can only take place at a higher concentration in the atmosphere
So the increase in flows to and from land and sea has natural causes. Emissions from the sea and the soil respiration are temperature sensitive. Due to the increase in the average global temperature of about 1 °C, these flows have grown by about 30 PgC/yr since 1750.
The absorption flows have also increased, with concentration being the driving factor. At sea, absorption increases with a higher concentration in the atmosphere based on Henry’s Law. On land, the higher CO₂-concentration makes the earth greener: plants grow faster when there is more CO₂. This causes a higher NPP (Net Primary Production) and therefore more absorption.
Or to put it in another way: the larger down-fluxes to land and sea are only possible due to higher concentration in the atmosphere. Also in a situation with no human emissions at all, but still a similar temperature rise (like e.g. in the Middle Ages), the CO₂ concentration would have to go up.
The following graph (Figure 6) shows again the main atmospheric flows, but now with the main driving forces.
It’s also obvious from this picture that it makes no sense to assume that human CO₂ accumulates in the atmosphere, as the IPCC says. It would be very illogical if the down-flux under the influence of the higher concentration does increase for natural CO₂, but not for human CO₂. Nature does not distinguish between human CO₂ molecules and natural ones.
The IPCC still makes a distinction between residence time and adjustment time, where the adjustment time is defined as the time for atmospheric CO₂ to re-equilibrate following a perturbation. In their view the adjustment time is much longer than the residence time. But such a distinction makes no sense as all the (natural) sinks treat all CO₂-molecules in the same way. If the oceans can absorb more CO₂ based on Henry’s law, they will do that for both natural and human CO₂. The fact that in the ocean all sorts of biological and chemical processes take place is perhaps interesting, but not at all relevant. There is no separate drain for human CO₂.
To summarize:
- The 1 °C increase in the average global temperature has resulted in a higher annual natural emissions from land and sea.
- This increase in natural emissions is also visible in figure 6.1 of AR5 (+30 PgC/yr).
- The increase in both natural and anthropogenic emissions has led to more CO₂ in the atmosphere.
- The higher concentration results in a greater down-flux to both sea and land.
- The increase in concentration in the atmosphere is the result of a combination of increased temperature and human emissions.
The calculated impact of human emissions
In 2019 Hermann Harde[5] worked out a calculation model to determine how great the influence of humans is on the rise in CO₂ and how great the influence of temperature is. In doing so, he applied the following principles:
- The CO₂ concentration in 1880 was 280 ppm (parts per million).
- Human emissions have gradually increased to 10 PgC/yr (based on emissions data).
- The flow of CO₂ from land and oceans to the atmosphere has increased proportionally with the increase in temperature.
- The annual absorption of CO₂ in is proportional to the concentration in the atmosphere. There is only one residence time for all CO₂.
It turns out that this simple model does an excellent job in describing the increased concentration in the atmosphere and also provides logical explanations for all the other observations made so far. In the following chart (Figure 7), the blue line shows the concentration increase due to anthropogenic emissions (human CO₂) and the purple line the concentration increase due to emissions due to increased temperature. The green line is the sum of the two. The green line corresponds well with the measurements in Mauna Loa (blue blocks).
It turns out that the impact human emissions on the CO₂-concentration is relatively small. In his calculations, only 17 ppm (less than 15%) of the total increase is due to human CO₂. The vast majority of the increase is the result of the increased global temperature.
The good correlation in the chart in Figure 7 is of course no proof of Harde’s model. As to speak with Richard Feynman: “We can’t prove anything. We can only disprove something.”. But at least his model is in line with the observed drivers of natural emissions and absorptions and similar to many other well-known physical processes. Unfortunately, that cannot be said about the standard model the IPCC is using.
References
- Chen et al.: China and India lead in greening of the world through land-use management, 2019.
- Friedlingstein et al., Global Carbon Budget 2020, 2020
- Harde: Scrutinizing the carbon cycle and CO2 residence time in the atmosphere, 2017
- Harde: Reply to Comment on “Scrutinizing the carbon cycle and CO2 residence time in the atmosphere”, 2017
- Harde: What Humans Contribute to Atmospheric CO2: Comparison of Carbon Cycle Models with Observations, 2019.
- IPCC: Fifth Assessment Report, 2013
- Jaworowski: CO2: The Greatest Scientific Scandal of Our Time, 2007
- Lee: Monitoring soil respiration using an automatic operating chamber in a Gwangneung temperate deciduous forest, 2011.
- Murray Salby presentation in Hamburg: What is Really Behind the Increase of Atmospheric CO2?, 2018
- NOAA, National Centers for Environmental Information: Map of Total Sea-Air CO2 flux
- Peng Li et al.: Quantification of the response of global terrestrial net primary production to multifactor global change, 2017.
- Stauffer, Berner: CO₂ in natural ice, 1978
- Zhang et al.: Rising soil temperature in China and its potential ecological impact, 2016.
- NASA: Carbon Dioxide Fertilization Greening Earth, Study Finds (website)
If there has been a net increase in the natural flow of CO2 to the atmosphere, then it would be additive to the anthropogenic flow. However, the increase in CO2 in the atmosphere is less than the known anthropogenic flow, which must mean a net decrease in the natural flow. There is no other explanation.
This is very poor reasoning. The sinks dynamically adjust to the inputs. It’s not a simple accounting exercise.
Bart, the sinks indeed adjust to the inputs, but not 100%. That is the point.
Sinks increase proportional to the extra CO2 pressure (pCO2) in the atmosphere above the average pCO2 of the ocean surface. The latter is around 295 μatm for a dynamic equilibrium between ocean surface and atmosphere at current ocean surface temperatures. The atmosphere currently is at 415 μatm.
The ΔpCO2 difference of 120 μatm is the driving force to push about 2.4 ppmv/year CO2 into oceans and vegetation.
As human input is near 5 ppmv/year, the net result is an increase of around 2.6 ppmv/year…
Indeed, it is a simple accounting exercise…
Darn, out of popcorn again. The fun, and funny part about this whole argument is that Skeptics/Climate Realists don’t even need the idea that humans aren’t responsible for the uptick in CO2, but the Alarmists surely need the idea that we are. The null hypotenuse appears to be that man is primarily responsible for the increase, but debate about it is certainly healthy from a science perspective. I don’t really care, except that it is nice to think that mankind is actually helping the planet by adding beneficial plant food, and thus greening the planet.
“The null hypotenuse”
OMG LOL !! Now that’s funny! Thanks for so comically demonstrating a lack of scientific acumen, Bruce.
” … appears to be that man is primarily responsible for the increase, but debate about it is certainly healthy from a science perspective.”
Uh, no, such debate is not healthy. Debating such an obvious fact, that can be clearly demonstrated with little more than grade school arithmetic, is willfully ignorant and stupid.
It was a joke, you moron. You obviously have no clue about what science is, or how it works.
Whether “hypotenuse” was a joke or not, Bruce, “debate” about this issue remains unhealthy. It is willfully ignorant and stupid. Simple grade school arithmetic easily demonstrates that the CO2 increase is entirely due to human emissions.
You are assuming it wasn’t purposeful, or a gift from MS Spell Check. Once again, you are reaching conclusions unsupported by any evidence. It seems to be a problem that you have.
Regardless whether “hypotenuse” was intentional or a “spell check gift”, Clyde, “debate” about this issue remains unhealthy. It is willfully ignorant and stupid. Simple grade school arithmetic easily demonstrates that the CO2 increase is entirely due to human emissions.
I do not believe anyone here has said somewhere what the real reason is as to why the CO2 is going up. The arctic seas are warming at a rate of around 0.7K per decade. See Table 2, https://breadonthewater.co.za/2022/03/08/who-or-what-turned-up-the-heat/
This causes a decline in the area where CO2 would normally sink:
CO2 + 2H2O + cold => HCO3- + H3O+
Now why is the arctic warming so much?
That is the question.
If the oceans are net releasing CO2 to the air, then why is the atmospheric increase in CO2 less than the anthropogenic increase?
Tom
About 1000 billion tons of CO2 are gassing out from the oceans, annually, mostly from around the equator.
To keep a balance, a similar amount must dissolve again at the poles. Do I think the 30 odd billion tons of CO2 annually from mankind is a big factor in any equation?
No.
The area in Antarctica where the CO2 dissolves has remained stable over the past 4 decades. The problem lies in the Arctic. Every year it warms there by another 0.05 – 0.07 C if not more. That means the areas where the CO2 must sink, is getting smaller. That explains also the zig-zag and the increase in CO2 in the atmosphere.
The question is why it has warmed so much in the arctic.
The fact remains that on any time frame you want to look at, there is less of an increase in the amount of CO2 in the atmosphere than the amount of manmade CO2 that is going into the atmosphere. The only way that works is if all the other CO2 flows are net going from the atmosphere to the land and oceans. The natural fluxes are much larger than the manmade contribution, but for the increase in the air to be less than the manmade contribution, the natural fluxes must be net negative with respect to the air.
Tom, you cannot compare the ‘past’ with the present where the past is always in proxies. I think I only read a few days ago that we cannot trust the ‘air bubbles’ in the ice samples as they do not contain the ‘correct” CO2 content of the time represented. In fact, there were quite a few measurements by scientists done at the beginning of the 19th century where values of around 400 were obtained.
OTOH
you are ignoring the big picture which is taking into account
all the CO2 in the air
all the CO2 dissolved in the oceans
all the bi-carbonates dissolved in the oceans
all the carbonates dissolved in the oceans
all the less soluble carbonates lying all over on the bottom of the oceans
which all interact and stand in equilibrium with each other. Man’s contribution to all the reactions going on, is, to say the least, ridiculously small compared to the complete carbon cycle,
and that is the reason why we are alive.
Cheers!
Oh. Forgot.
Why is it getting so much warmer in the Arctic and also in and around the Black Sea?
HenryP,
It doesn’t matter how much C species is in any reservoir, as long as it stays there.
It doesn’t matter how much C species are exchanged between the reservoirs, as long as the influxes equal the outfluxes.
Only the difference between influxes and outfluxes matters.
And nature provides more outflux than influx, thus is not the cause of the increase in the atmosphere. No matter if human emissions are 0,1% or 1% or 10% of all the fluxes that are passing by but don’t contribute to the increase.
Ferdinand
That is my point, is it not.
It does not stay there.
Every reaction of the co2 and the carbonates are in equilibrium and depending on pH, temperature and pressure the equilibria shift…..
This has almost nothing to do with the past.
Over the next year, we will add X amount of CO2 to the air from burning fossil fuels.
But the amount of increase in the entire atmosphere will be a fraction of X.
That has nothing to do with the past, and nothing to do with any other place that CO2 is being added to the air.
On the basis of the simple fact of the net gain in the air being less than our known additions to the air, it is a plain matter of simple arithmetic that more is coming out of the air than what is going into it.
We do not need to know anything about the other amounts to make this simple observation of obvious and simple addition and subtraction mathematics.
It amazes me that people cannot or refuse to understand what you just said.
“It amazes me that people cannot or refuse to understand what you just said.”
Ditto.
I can hardly believe we are needing to repeatedly point this out.
It is so obvious that something else must be going on besides what those of us making this point over and over again are saying.
Do you understand now what the reason why CO2 is increasing in the atmosphere?
Due to temperature, pH and pressure related issues there is more CO2 gassing from the oceans than that what sincs at the poles. Simple analytical and physical chemistry.
Maybe you should study it.
Henry said:
“Do you understand now what the reason why CO2 is increasing in the atmosphere?
Due to temperature, pH and pressure related issues there is more CO2 gassing from the oceans than that what sincs at the poles. Simple analytical and physical chemistry.
Maybe you should study it.”
Everyone who has their brain turned on knows who needs to go back to school.
Start with learning to spell.
What you claim is a matter of “simple” analytical and physical chemistry is actually a matter of measuring net fluxes from entire oceans on a planet, and every other source and sink on earth that is part of the carbon cycle.
You are making assertions, not doing chemistry.
Speculation is not synonymous with science.
At the same time you are stubbornly ignoring what is being said to you, and bizarrely claiming that the only two parameters that we have a good handle on, and which are the relevent facts in the entire discussion, do not matter.
Are you being willfully obtuse, or are you incapable of comprehending what is being argued to you?
Because you have not responded a single time to the actual matter being discussed, which is that the amount of increase in CO2 per year is LESS than what humans are adding by burning fossil fuels.
You are saying there is another larger source, and so fossil fuel emissions are irrelevant, and refuse to respond when it is pointed out that you are not making logical sense.
Has nothing to do with the past. If we measure the increase in the quantity (mass) of CO2 in the air between now and a year from now, we will find that the increase in the amount is less than the amount of manmade CO2 emitted into the atmospheric during that same length of time. This can only be true if the sum of all the other CO2 flows is negative (positive is going from the land or sea to the air, and negative is going from the air to the land and sea.) This is due to the law of conservation of matter; a principle of physics that is inviolable. There is no other fact or information that you can bring to bear on this question that will change the answer, unless you can show that our measurements of the CO2 in the air are wrong, or the calculated amount of manmade CO2 is wrong, or the value we have for the mass of the atmosphere is wrong. Any other facts you may wish to bring up are irrelevant.
All the CO2 in the oceans doesn’t count as long as it stays there.
No matter how much CO2 is moving between the different reservoirs, as long as the inputs equal the outputs nothing happens with the amounts in the reservoirs.
Only the difference between inputs and outputs matters and that is only half human emissions, no matter how small that is…
Ferdinand
That is my point, is it not.
It does not stay there.
Every chemical reaction of the CO2 and the carbonates are in equilibrium and depending on pH, temperature and pressure the equilibria shift…..
The billions of tons of CO2 that gas out naturally from around the equator
HCO3- + UV/heat => CO2 + OH-
must dissolve again in the pole areas. If there is a change in sink area than that must be the first suspect for your increase in CO2 in the atmosphere.
CO2 + 2H2O => HCO3- + H3O+
Ja. Ja. Ferdinand. You were the one who started all this CO2 nonsense. I remember that I told then and I will tell you now again: you cannot ‘calculate’ what you cannot measure.
But you can measure it?
What you do amounts to hand waving, but you seem to have no ability to use logic.
HenryP,
Lots of measurements were done all over the oceans in the past centuries. They show that
Thus the observations show that the Oceans are a net sink for CO2, but you insist that’s not true, so where is your evidence?
Sink rates not only depend of sink area, they depend of the pCO2 difference, which largely increased over time…
pH and DIC measurements at several ocean stations:
https://tos.org/oceanography/assets/docs/27-1_bates.pdf
Oil pollution.
JF
Julian, have you got the test results to prove that?
Because my test could not find a definitive answer to that question.
(Click on my name to find my report on that)
So what if it’s going up, all that means is we’ll have a greener planet. The Earth could not survive without CO2.
All this research about how much CO2 is in the atmosphere and what caused it is a self eating snake; considering that there is no emperical evidence that CO2 in the concentrations that can or have existed have any effect on climatic temperatures. It is a ” Tuesday follows Monday therefore Monday caused Tuesday” claim.
No observed evidence that CO2 has a net direct effect, no; but, rather indirectly through greening the Earth.
True. But is the warming due to extra greening the only reason for earth to get warmer?
The warming, cooling, change, yes. It’s the green house effect: lush, moist, and closed. That, and the irregular impulse functions (e.g. blocking, phase shifts) that distort our record keeping.
You still have not understood why the CO2 in the atmosphere is going up. Let me say it again. It is because the sinc area in the arctic is getting smaller and smaller.
You’re doing a great job, HenryP. But, it’s impossible to get through to Ferdinand. He’s still pushing that ridiculous pseudo-mass balance argument. He just does not understand dynamic systems. I gave up trying to get through. It’s a waste of time.
Hey Bart, still alive I see…
For those who don’t know our history of discussions in the past:
His natural increase was based on the synchronous variability and trends of temperature and the derivative of CO2. Which is bad science: compare variables of the same order (direct with direct, derivative with derivative) and as they changed synchronously, that doesn’t show which one leads the other.
What he did forget is that for sinusoidal variables the variability of the variable and its derivative is mostly the same, but the latter is 90 degrees shifted to the left…
Moreover short term CO2 variability is caused by short term temperature variability with the main response by vegetation (as is proven by the opposite CO2 / δ13C movements), but the trend in vegetation is more uptake than release with higher temperatures, thus vegetation is NOT the cause of the increase…
Frans, here my next comments:
“As early as 1978, Stauffer and Berner[12] concluded: “We estimate the fraction of CO₂, present in bubbles to be only about 20%. The remaining part is dissolved in the ice.” Other scientists such as Jaworowski[7] and Harde[4] have also discussed major imperfections of ice core measurements in various publications. Contrary to what is often assumed, the ice layers are not a closed system. The air in the air bubbles in the deep ice layers no longer has the same composition as when the air bubbles were formed.”
The work of Stauffer and Berner is from 1978, in the begin period of ice core measurements. They assumed that most of the CO2 was in the ice, as they melted all ice and it did take a lot of time to extract all CO2 (because of the slow diffusion of CO2 in water and the chemistry involved). CO2 can’t pass the ice matrix, it only may adhere to the ice surface or in liquid-like veins in between the ice crystals.
Later the melting of ice for CO2 measurements was completely abandoned, especially for Greenland ice, as there were reactions between carbonate deposits in the ice and highly acidic dust from nearby Icelandic volcanoes. Nowadays for high resolution measurements all ice is sublimated and 99.8% of all CO2 is recovered, wherever it may reside, even from clathrates. Moreover, there is very little water left at -23°C in coastal ice at Antarctica and nothing at -40°C for inland ice like Vostok and Dome C.
And let Jaworowski rest in peace, together with his wrong ideas about CO2 in ice. He never performed any CO2 measurements, only looked at radioactive isotopes in ice, but these may migrate through the ice crystal matrix, CO2 can’t do that.
All his objections were already rebutted in 1996 by three ice core drillings at Law Dome, published by Etheridge e.a. Still Jaworowski repeated his wrong statements in 2007…
See my comment on Jaworowski:
http://www.ferdinand-engelbeen.be/klimaat/jaworowski.html
About Harde, see my rebuttal at:
http://www.ferdinand-engelbeen.be/klimaat/Harde.pdf
“it makes no sense to assume that human CO₂ accumulates in the atmosphere, as the IPCC says.”
The IPCC never said that (or not as you think they mean): all increase of CO2 is caused by humans, that is what the IPCC says (and is true) and it takes time to remove that from the atmosphere. That is all. No matter what the origin is of the CO2 molecules left in the atmosphere. It is about the extra mass of CO2 above the equilibrium of the ocean surface with the atmosphere for the current average sea surface temperature, which is around 295 ppmv, not 415 ppmv…
Ferdinand
You have not and for some reason do not want to understand the real reason why the CO2 content of the atmosphere is rising.
HenryP, I do look at all available evidence and did that already near twenty years ago. If all observations agree with the human cause and none refutes that, then in my opinion that is the real reason for the increase.
After years of discussion, I have put that all in a web page to read for anyone:
http://www.ferdinand-engelbeen.be/klimaat/co2_origin.html
That was in 2007, already 15 years ago. Since then nobody did refute any of the arguments and that humans are to blame still stands strong.
All alternatives I have read violate one or more observations, thus are refuted, not at least by the mass balance…
Take your own argument:
It may be true that the sink area at the poles is shrinking (but I haven’t seen any evidence for that). But let us assume that there is a 10% loss of area. As CO2 in the atmosphere is increasing, you need an additional 10% increase of CO2 to fully compensate for the loss in area. That is an increase of about 12 ppmv in the atmosphere, reached in only 5 years of current human emissions and current sink rate… Still human emissions are the only source of the increase in the atmosphere…
I am sorry Ferdinand, but this is not at all convincing. Please have a look on what I have written about this. https://www.klimaatfeiten.nl/co2/co2-stijging/co2-hockeystick
Dear Frans,
If all you have is a critique on what ice cores show as CO2 levels, a critique that mainly is based on points of 40-50 years ago, which point by point were refuted or corrected over time, then you have no real arguments.
As a simple example:
“The air in the air bubbles in the deep ice layers no longer has the same composition as when the air bubbles were formed.”
If that was true, do you really think that CO2 moved from 2 km deep to the surface to escape? Even if there was some migration from layer to layer, that smooths out some variability, but that doesn’t change the average level over longer periods. If other methods like stomata proxy data show different CO2 averages over the same period as the resolution of the ice cores, the stomata data need recalibration against the ice core data, not reverse.
For the 800,000 years Dome C ice core, only the modern sublimation technique was used to determine CO2 levels. Recovery of CO2, N2, O2, N2O,… over 99.8%. Where should CO2 hide to get unmeasured?
https://www.researchgate.net/publication/253089968_A_sublimation_technique_for_high-precision_measurements_of_d13CO2_and_mixing_ratios_of_CO2_and_N2O_from_air_trapped_in_ice_cores
Another point are the historical CO2 measurements in the atmosphere:
“Tussen 1812 en 1961 zijn op vele plaatsen in de wereld meer dan 90.000 directe metingen uitgevoerd”
In English:
“Between 1812 and 1961 at many places on earth over 90.000 direct [CO2] measurements were performed”
Most were compiled by the late Ernst Beck. The problem is not the performance of the old measurements (+/- 10 ppmv if correctly performed), the problem was where was measured:
In the middle of towns, in forests, between growing vegetables (!), etc… where you can measure between 250 and 600 ppmv, depending of the time of the day, sunlight and inversion when there is no wind…
See my critique on Beck’s compilation:
http://www.ferdinand-engelbeen.be/klimaat/beck_data.html
The data taken on board of sea ships or coastal with wind from the sea all are around the ice core data…
Thus please, be as critical for the alternative data as for the ice core data themselves and if you do that, most alternative data are simply inferior to the ice core data…
Perhaps you should read the interesting article of Andy May on this subject on this website: https://wattsupwiththat.com/2021/01/15/the-co2-kink-firn-to-ice-transition/
His conclusion:
“As atmospheric CO2 passes from firn to ice, it is altered due to gas mixing processes and compaction as discussed above. Most CO2 graphs are presented using a simple splice of modern atmospheric CO2 measurements onto Antarctic ice CO2 data. The necessary corrections for attenuation of CO2 in ice due to gas mixing and depth of burial are not applied or even noted. By neglecting these corrections, resulting plots are misleading and amplify the difference between modern and older ice core CO2 measurements such as this one on Scripps’ website. Beware of the CO2 Kink, it is not a real atmospheric signal, it is an artifact.”
It’s always easy to deny measurements that do not fit the preferred outcome. My own conclusion on these measurements was the following:
“It is difficult to estimate how reliable the various measurements are. There will undoubtedly be measurements that give a distorted picture, for example due to local influences on the measurement set-up. At the same time, it involves scientific publications by respected scientists and uses measurement techniques, the reliability and accuracy of which are fairly well known. In any case, the results indicate that the variety in measured values is greater than the ice core measurements suggest.”
Frans,
Don’t look only at what you like in an article, but also look at the critique in the comments…
I have commented there at that time and as said there:
Etheridge e.a. measured CO2 levels in still open pores of the firn and already closed bubbles in the ice at the same depth and found the same CO2 levels, thus there is no fractionation of CO2 when the bubbles are closed. But there is some fractionation for O2, Ne, Ar and other small molecules (for the differences in vibrational diameter).
There is a 20 year (1960-1980) overlap between direct measurements at the South Pole and the ice core measurements of Law Dome. They show the same CO2 levels for the same average age of the air in the ice bubbles within 1.2 ppmv (1 sigma).
Thus the “CO2 kink” is real and not caused by fractionation of CO2 at the moment that the bubbles closed.
Have you read my critique on the compilation of the late Ernst Beck?
I have had several years of discussions with him about that subject. Beck lumped all measurements together: the good, the bad and the ugly. Only after al lot of discussion he removed the ugly data, but still insisted to include all bad data.
Like at Misra (India), where they measured CO2 levels under, in between and over leaves of growing crops. Nothing to do with global CO2 levels, but still included in his compilation…
We all have a lot of critique on climate science for using thermometer measurements in the middle of towns, without taking into account the growing UHI effect over time.
But you do endorse exactly the same for the past CO2 data…
Callendar was a smart guy who used a priory criteria to remove any CO2 data that could be contaminated by local sinks and sources: like “don’t use data taken for agricultural purposes”, which avoids such a mess…
Thus sorry… again look at the data that you like as critical as to the data you don’t like and if the data you don’t like are more reliable than the other data, then accept them… That is what real scientists do…
“the IPCC-models calculate with a small residence time of about 4 years for natural CO₂ and a large one for human CO”
This is a common misunderstanding.
IPCC calculate with a small residence time for CO2 up to 280 ppm (so called equilibrium value), and a much longer residence time for CO2 above 280 ppm.
The model does not make any difference between “human” and “natural” CO2.
However, since human emissions add to the atmospheric CO2 above 280 ppm, it will stay for very long time. Any extra contribution (e.g. from volcanos) would stay very long according to IPCC.
JonasW,
The IPCC is right to make a differentiation between residence time (about 4 years) and excess decay rate of any extra CO2 (whatever the source) above the equilibrium between ocean surface and atmosphere.
But the IPCC is completely wrong about the long times needed to remove that extra CO2: the measured decay rate is slightly above 50 years, that is all.
The problem with the IPCC is that they use the Bern model or similar models, which assume a saturation of different reservoirs. That is only true for the ocean surface, not for vegetation (only beyond 1,000 ppmv) and absolutely not for the deep oceans, which have small direct connections with the atmosphere near the poles, where no saturation is in sight for hundreds of years to come…
I do not agree. IPCC makes a differentiation – that is correct, but the differentiation is based on the Revelle factor. The Revelle factor reflects the so called saturation (or buffering).
A lot of people have told me that the Revelle factor is based on sound physics/chemistry. I strongly doubt this.
My questions are:
1-how do they calculate the Revelle factor? The exact equation behind the Revelle factor. It is not measured -it is calculated from salinity and pH. The equation!!!
2- where are the experimental support for the Revelle factor. If there is a saturation effect, it should be very easy to verify that in a laboratory experiment.
Take a bucket of sea water equilibrated with a 280 ppm atmosphere. Add some CO2 and show the saturation effect (= revelle factor).
JonaW,
The Revelle factor can be measured and can be calculated… Its formula is here:
https://en.wikipedia.org/wiki/Revelle_factor
They have done these experiments and even better, they have taken thousands of seawater samples and measured it and again better than that, there are a few stations where they have several decades of seawater measurements at the same place.
If you look at the increase in the atmosphere and the increase of DIC in the ocean surface in over the same period, you will see that the increase of DIC in seawater is only around 10% of the increase in the atmosphere…
The figures for DIC can be found in Table 2 of:
https://tos.org/oceanography/assets/docs/27-1_bates.pdf
Ferdinand,
No, there is no equation given in the reference. They only give a definitio, without any explanation how they calculate the value..
They calculate R (=Revelle factor) from salinity, alkalinity and pH.
I am asking for an equation of the type R=f(alkalinity,salinity,pH), where they describe the function f.
No, there are no direct measurements of the Revelle factor. Only indirect measurements through the variables described above. Then they calculate the Revelle factor.
As I wrote, it would be easy to do a direct measurement.
The statement is that sea water equilibrated with a 280 ppm CO2 atmosphere is saturated, meaning that additional CO2 in the atmosphere has “problems” to be absorbed by the sea water.
That experiment should be done. A tank partly filled with sea water and a controlled atmosphere above. Start with CO2 concentration of 280 ppm, and increase the CO2. Measure the CO2 absorbed by the sea water.
Then it is straightforward to determine the Revelle factor with the governing equations in the Bern model.
I am pretty sure that it will give a value of R about 1, since an R value significantly greater than 1 is in direct conflict with Henrys law.
JonasW,
If U use the formula given in the reference:
Revelle factor = Δ[CO2]/[CO2] / Δ[DIC]/[DIC]
you can use that to get the Revelle factor directly as all parts are measured values.
Take the figures for Mauna Loa and Bermuda 1983-2012:
Mauna Loa:
+50 ppmv over 391 ppmv
Bats (Bermuda):
+32.5 μmol/kg/year over 2050 μmol/kg/year2
That gives for Bermuda over that period:
Revelle factor = 50/391 / 32.5/2050 = 8.07
Bates used a different definition for the Revelle factor, where they use the logarithm of the change. That gives a Revelle factor of around 9 in Figure 6 of the reference I did give.
They also give some background of the different calculations in Box 1, page 128.
A Revelle factor of about 1 you can’t find in seawater: pure dissolved CO2 follows the atmospheric changes per Henry’s law, but pure CO2 is only 1% of all DIC species, the rest of the reactions doesn’t follow changes in the atmosphere for 100%, more like around 10%…
I don’t have the formula they used to calculate the Revelle factor out of DIC, total alkalinity etc… But it is known that if you have 3 or 4 measured parameters in seawater, you can calculate all other factors. That is e.g. the case for the pH, which ancient measurements with glass electrodes were too coarse. They compared calculated pH and measured colorimetric pH over several decades at HOT (Hawaii) and these match…
My question is how you calculate the Revelle factor from alkalinity, salinity and pH.
I do know that Revelle factor = Δ[CO2]/[CO2] / Δ[DIC]/[DIC]
You say that “But it is known that if you have 3 or 4 measured parameters in seawater, you can calculate all other factors.”
It would be very informative if you explain how you calculate all the other factors. Please explain in detail if it is known – where can I find a detailed clarification of how “all other factors” are calculated from 3 or 4 measured parameters?
I assume that you in reality know that there is no equation behind the calculation of the Revelle factor. It is only statements like “you can calculate all other factors”.
No details, no equations, no facts – but “overwhelming proofs”.
The Revell factor can be determined from rather simple solubilty experiments. Do you support that those experiments should be done ?
JonasW,
That experiment was done in the real world and the Revelle factor was calculated from all available measurements.
But feel free to do your own experiments, if you don’t believe the figures they provided.
About the calculation of other parameters from known parameters, here an example of pH calculated from total alkalinity and DIC (and “a few” other things):
http://www.astro.ulg.ac.be/~munhoven/fr/cours/modenv/current/Lecture_pH-Handout.pdf
Nice literature for specialists, but the results are quite accurate, as parallel measurements with the very accurate colorometric method (better than 0.0001 pH unit) are equal.
Here a good base for what can be done to calculate all other factors out of only two known factors of seawater. These calculation programs are used by all oceanographers, thus I suppose that these are based on sound science or the results would not reflect reality when measured vs. calculated…
https://en.wikipedia.org/wiki/CO2SYS
Hello Ferdinand,
Yes, those experiments has been done in the real world.. and the result is that the Revelle factor is one. Also called Henry´s law.
There is a lot of experiments saying the same thing – there is no “magical” buffering in sea water. Henry´s law applies to sea water.
I am asking for the equation between Revell factor and alkalinity, salinity and pH. I am not asking for an equation how to calculate pH. I am not interested in pH. I am interested in the Revelle factor.
JonasW,
Henry’s law only is applicable for dissolved, pure CO2. Not for bicarbonates and carbonates. Henry’s law is about gases in air and solution. Not ions.
Pure CO2 in seawater is 1% of all inorganic carbon, 90% is bicarbonates and 9% carbonates.
If CO2 in the atmosphere doubles, in seawater it doubles too: from 1% to 2%. The other species also increase, but don’t double, more like increasing with about 10%.
Here all calculations, including the code in R as used:
https://biocycle.atmos.colostate.edu/shiny/carbonate/
click on “chemistry”
Hello Ferdinand;
eh ? Henrys law is applicable for the equilibrium between a gas phase and the dissolved gas.
The amount of dissolved gas is proportional to the partial pressure of the gas.
It does not matter if the dissolved phase is bicarbonates, since the bicarbonates equilibrates with the dissolved CO2 (basic chemistry).
The Revelle factor says that the dissolved gas has an discontinuity at 280 ppm. Suddenly the dissolved gas is no longer proportional to the partial pressure. For some very mysterious reason the liquid can only dissolve 1/10:th of what it could dissolve below 280 ppm.
Admit it – it is crap. It is not science, It is propaganda.
I agree that you have a point when it comes to carbonates. There are two sources for carbon in the sea – one is the atmosphere equilibrium, and the other is dissolution of Calcium- Carbonates.
A few minutes calculation will show that the Calcium-carbonate source is negligible. It is so small that it has no significant effect on the carbon level in sea.
Just look at the amount of Calcium. That tells you how much carbon has on origin as Calcium-Carbonate.
Your link did not include any equation for the Revell factor ?
The truth is that no one can show how the Revell factor is calculated. The reason is that the calculation is fake.
If I give you values for salinity, alkalinity and pH – can you tell me what the Revelle factor is ?
Its is really great that the AGW drones and other lukewarmers and CO2-haters think that humans have caused all the highly beneficial rise in atmospheric CO2.
That would mean that, with China, India, and several other developing countries about to ramp up their release of sequestered carbon, that global emissions will continue to rise, and so atmospheric CO2 concentrations will also continue to rise.
The really beautiful thing about this, is that there is absolutely nothing that they can do about it 🙂
All that the cuts in CO2 emission in once-first-world couttries has accomplished is to destroy the electrical supply systems of those countries, while transferring CO2 emissions to developing countries.
Be nice.
Tell me that at least you do understand why the CO2 is going up in the atmosphere.
Oh dear. I am an idiot. Or you all are.
Ferdinand
Let me pick on one point which you brought up yourself:
Now, note that even though the water of the oceans have not gone acidic, a lower pH means that there is more available hydronium ion in the water. That means that the balance is disturbed,
H3O+ + HCO3- => CO2 (g) + 2H2O
so that more CO2 is coming into the atmosphere.
The HCO3- concentration is constant, because the other equilibria – concerning the soluble and less soluble carbonates – all shift up.
So clearly, a lower pH means that more CO2 goes in the air. So, has anyone (by now) studied how much extra ppm is coming into the atmosphere due to lower pH?
See what I am saying?.
The other two unknowns are temperature and pressure. We know that the temperature increase in the Arctic has been dramatic. So, has anyone (by now) studied how much extra CO2 is coming into the atmosphere due to the reduction of sink areas there?
See what I am saying?
We don’t even know if pressure is constant. It appears that the volume of the atmosphere is in fact not constant. It depends on the sun.
See what I am saying?
Too many unknowns.
Case closed.
But we can say that the increase of CO2 in the atmosphere is most probably due the decrease in the sink area in the Arctic, because here we find the biggest delta T inside the Arctic seas. (see Table 2 of my report, click on my name)
“So clearly, a lower pH means that more CO2 goes in the air”
No, it is because the CO₂ concentration in the air has been forced higher. The reaction you write is a two-way dynamic equilibrium,
H₃O⁺ + HCO₃⁻ ⇌ CO₂ + 2H₂O
and adding CO₂ to the air pushes it to the left, lowering pH. The [CO₂] in water is higher, not lower.
Nick
That is the wrong argument, in this case. You cannot argue it two ways. I am saying that if the concentration of the hydronium ion goes up and bi-carbonate stays at the same concentration, CO2 must go up. That is basic analytical chemistry.
Which brings me back to my original argument.
https://wattsupwiththat.com/2022/04/22/why-is-the-co%e2%82%82-concentration-rising/#comment-3504361
Do you understand now what is forcing the CO2 up in the atmosphere? It is the diminishing sink areas in the Arctic due to the high rate of warming there.
However bicarbonate ion concentration does not stay the same as can be seen in the Bjerrum plot which is the result of Henry’s law dissolution of CO2 and chemical equilibria:
CO2 + H2O ⇌ H+ + HCO−
HCO−3 ⇌ H+ + CO2−3
440px-Carbonate_Bjerrum.gif
Henry,
“I am saying that if the concentration of the hydronium ion goes up and bi-carbonate stays at the same concentration, CO2 must go up.”
You can think of it in Le Chatelier style. The action was to burn a whole lot of reduced carbon fuels. That increases CO₂ in the environment. Something happens to oppose that. Some reacts with water, generating H₃O⁺. A much larger amount reacts with the stronger base carbonate (buffering). But these are all responses to mitigate the original action. The amount of CO₂ remaining is still higher; the mitigation is only partial.
Henry,
“I am saying that if the concentration of the hydronium ion goes up and bi-carbonate stays at the same concentration, CO2 must go up.”
You can think of it in Le Chatelier style. The action was to burn a whole lot of reduced carbon fuels. That increases CO₂ in the environment. Something happens to oppose that. Some reacts with water, generating H₃O⁺. A much larger amount reacts with the stronger base carbonate (buffering). But these are all responses to mitigate the original action. The amount of CO₂ is still higher; the mitigation is only partial.
HenryP,
You are swapping cause and effect.
If there was a problem with the sink areas, the linear ratio between the net sink of CO2 and the extra CO2 pressure (pCO2) above equilibrium (currently 120 μatm over the globe) should decrease, but there is no sign that the uptake did decrease, to the contrary…
Further, Henry’s law counts for each species on its own: the partial pressure of CO2 on its own is what counts, no matter if that is withinin 99.996% air pressure or in near absolute vacuum (as long as water is not boiling)… Of course, if the air pressure sinks, then the pCO2 also sinks, but the difference in air pressure is small (+/- 3%) and the average returns in a matter of days…
Ferdinand, Phil.
This is where it gets a bit more complicated. Now you say:
‘carbonates get lower, bicarbonates hardly change’
and Phil. maintains that even the bi-carbonate concentration is not constant.
This is where you both are wrong. What you people are forgetting is that there are (also) billions of tons of poorer soluble carbonates lying on the bottom of the oceans. They are also all in equilibrium states, e.g.
CaCO3 => CO3– + Ca++
So, now: what happens if you remove CO3– from the top? You have disturbed the equilibrium so more CaCO3 will go into solution. The same for MgCO3, etc.
In effect, what I am saying, is that there is virtually an endless buffering action as far as the carbonates in the oceans is concerned. You cannot change the carbonate or bi-carbonate concentrations, anyway, anyhow. Perhaps that is also the reason why we are all alive today.
HenryP, you are moving the goal posts. The question was that you insist that a lower pH causes more CO2 to be released, but it is just the opposite: the higher CO2 in the atmosphere causes more CO2 and bicarbonates and carbonates and a lower pH in seawater.
The Bjerrum plot only shows relative quantities in % not absolute quantities.
If seawater gets more acid, all DIC species get lower.
If more CO2 is pushed into the oceans, because of the higher CO2 pressure in the atmosphere, then all DIC species get higher.
Carbonate rock at the bottom of the oceans plays no role at all in these equations…
Oh. So you think that the waste water of 7 billion people and even more cattle and animals and all our factories is of no consequence?
If you are lucky and if people keep to international rules the pH of that waste is not lower than 6, but I doubt if people in the east are as conscientious as people in the west about that.
As I said, if the pH of the sea water goes down, more CO2 will get in the air as the carbonate content does not change. If the temperature of the sink areas goes up -as dramatic as in the Arctic-, more CO2 will go up in the air. If the pressure goes down, due to changes in the volume of the atmosphere, that too could also be a cause of more CO2 in the air.
It is not I moving the goal post. It is the people proposing that more CO2 is not good that bury their heads in the sand. Just like the ostriches here.
HenryP,
What people do with their waste water is not the subject of discussion… Again you are diverting the discussion to irrelevant points, as waste water is only relevant for rivers and estauria, not the bulk of the oceans. Neither are undersea volcanoes, despite blowing a lot of SO2 and CO2 into the deep oceans.
All what counts is that in the surface waters DIC increases while the pH decreases. That proves beyond doubt that the CO2 flux is from the atmosphere into the ocean surface, not reverse…
Let me summarize:
Ferdinand, it was you who said that the pH of the oceans is getting lower. You (and others) think it is the (extra) CO2 from man doing it
I said: other than more heat in the water – especially noticeable in the Arctic – , a lower pH would also be a sure reason for more CO2 in the atmosphere, given that by my reasoning the carbonate and bicarbonate concentration of the oceans are constant because of the unending buffering action by the less soluble carbonates, of which there is an unbelievable abundance. Unlike you, I note that all rivers, lakes and estuaries eventually always do end up in the oceans. So if the pH of the oceans are going down it is most probably because of the waste water of mankind.
I suppose there is only one way to settle this dispute. Do we have measurements of the carbonate content over time?
HenryP, if the pH lowers, there are less carbonates in % (not necessary in total quantity), compared to bicarbonates and carbonates.
If the pH lowers due to wastewater or undersea volcanoes, then DIC as total CO2 + bicsrbonates + carbonates gets lower with lower pH as cause.
If the pH lowers due to excess CO2 entering the ocean surface, then DIC gets higher with lower pH as result.
The observations show that DIC increases while the pH decreases, thus the net CO2 flux is from the atmosphere into the oceans, not reverse…
Ferdinand,
now you say
The observations show that DIC increases while the pH decreases, thus the net CO2 flux is from the atmosphere into the oceans, not reverse…
Can I have a look at the measurements?
HenryP,
See:
https://tos.org/oceanography/assets/docs/27-1_bates.pdf
DIC measurements in Table 2 and Figure 3.
pH measurements in Table 2 and Figure 7.
Ferdinand
I have read the report, thanks.
But it seems to me they are arguing from the wrong point of view.
The way I see it they say: pH is going down and pCO2 is going up so it must be (our) CO2 who is doing it.
As far as DIC is concerned, their method is confusing to me. If I wanted to know total carbonate in a solution I would do a gravimetric measurement that is carbonate specific. There is also a simple acid -base method to determine HCO3- (first)
I am sorry. I don’t see any attempt to do some decent basic chemistry in your report.
The reaction that is relevant here is the equilibrium
CO2 + 2H2O + cold = heat + HCO3- + H3O+
which is restricted going to the right if the cold areas are getting smaller, like in the Arctic. Given that HCO3- does not change, more H3O+ ions (=lower pH) would naturally shift the reaction more to the left
To prove to me that the reaction has shifted right, due to the burning of fuels, you must simply prove to me that HCO3- has gone up.
I donot get that from your report.
PS
I hope you are not one of those people who say: ‘there must be something we are doing wrong’. You have to come come with good factual proof for anything to blame people.
For example, I have no idea how it was in the past, before man even came in the picture and started to drill for oil (was that in the 1930’s?) But I imagine that if lightning caused a big fire and there were no people around to extinguish it, that would have caused a lot of extra CO2 in the air….
Huge “prairie” fires have always dumped CO2 into the atmosphere. Be it on the plains of the central US or the sav
Henry,
Just a matter of calculations…
If DIC increases, that doesn’t give much change in HCO3- in percent (Bjerrum plot), but it does increase total HCO3-.
For measured increase of DIC in the past 29 years at BATS (Bermuda), which is 1.5%, the increase in HCO3- is at least 1.5% over the same time span.
Moreover, the Bjerrum plot shows a slight increase of HCO3- with lower pH, at the cost of CO3–
No need to separate the three C species for that calculation…
I have samples from the Indian Ocean every year we went there for a holiday. I have kept them in the dark in my office and they still look good. I have collected 6 years. Are you saying that I will find that HCO3- has increased over time and if so, by ‘your measurement’, by how much?
Complete nonsense. I doubt that I will find any change in HCO3- or CO3- in the big ocean.
Your plot is completely wrong because there is no CO3 that will disappear in the oceans. There is a never ending supply of poorer soluble carbonates from the bottom that will keep the CO3 completely unchanged.
HenryP, there are no sampling stations in the Indian Ocean, but as DIC is increasing everywhere, I am pretty sure that CO2, HCO3- and CO3– are increasing while the pH is decreasing in your samples.
The increase of HCO3- at the cost of CO3– is in percent, but both will rise, as the total rises, only HCO3- will rise faster than CO3–. No need for dissolution of carbonates from the seafloor, as the extra HCO3- and CO3– comes from the atmosphere, not the ocean bottom.
If I take the figures for HOT (Hawaii) as base for also the Indian Ocean, then the increase of DIC would be around 0.33%, HCO3- slightly higher and CO2– slightly lower than the 0.33% increase for total DIC.
pH drop would be about 0.01 pH unit.
With very good analytical instruments that should be measurable.
I am confident that my results will not show any change in bi carbonate or carbonate concentration simply because the carbonate content of the oceans is unchangeable. Any data you bring showing a changing carbonate concentration must be viewed with suspicion.
Any change from the top will be met by the opposite reaction from the insoluble carbonates lying on the bottom of the oceans bringing the carbonate back to where it was before.
That is the right ocean chemistry. There is no end to the buffering of carbonate in solution in the oceans.
If the CO2 in the atmosphere goes up is has to do with the pH and heat in the oceans, mostly.
It is actually amazing for me to see that our waste is causing more dung in the air making earth greener. The extra greening is trapping some heat.
HenryP,
There is no carbonate rock in the ocean’s surface layer to buffer any extra CO2 entering the ocean surface. The reaction (and the figures) are from atmospheric CO2 to DIC and lower pH. Not reverse.
If you are confident of the opposite, let your samples analyze in a specialized laboratory…
Surely, the earth turns and wobbles and the moon changes the tides to mix all the water and everything up. I also don’t think that the poorer soluble carbonate are all rock. I bet that I will find it if I analyze a sample from the sand. It is just as I say: the carbonate content in the oceans does not change. If you measured somewhere where it did change, it means your sampling is not representative…….
Whenever it changes on the top, like,
CO2 + 2H2O = HCO3- + H3O+
it forces the other reaction of the bi-carbonate to the right so that more carbonate is coming into solution. More carbonate
X CO3 = X++ + CO3–
forces the equilibrium of the poor soluble X carbonate to the left. Remember that the oceans are completely saturated with the poorer soluble carbonates like, for example, those of potassium, magnesium and calcium.
Basic chemistry.
PS
It seems you are getting worried about what my samples in my cupboard will show. I am thinking that 6 years for a time series is too small. I think I must still collect more samples.
Hi Frans, The fundamental mistake in your post is that you swapped the antropgenic en temparature contributions in your figure 7. Because from the vostok ice core the temperature dependency of co2 in the atmosphere can be determined, so the blue line is the temperature determined equilibrium concentration, which has slightly increased since LIA. The purple line is the antroprogenic contribution.
Can anyone tell me why some CO2 mappings based on OCO-2 data have shown the highest levels of CO2 on Earth to be at the locations of the most highly vegetative areas on Earth like the Amazon Rain Forest?
Because there is the biggest biological annual amplitude, but breathing is not what causes the co2 rise.
If the Amazon Rain Forest is a large CO2 sink then I still do not understand the presence of an elevated level of CO2. Wouldn’t the level usually be lower than that of less vegetative areas?
There is a huge interannual variability in the Amazon
Cramer, Wolfgang & Bondeau, Alberte & Schaphoff, Sibyll & Lucht, Wolfgang & Smith, Benjamin & Sitch, Stephen. (2004). Tropical forests and the global carbon cycle: Impacts of atmospheric carbon dioxide, climate change and rate of deforestation. Philosophical transactions of the Royal Society of London. Series B, Biological sciences. 359. 331-43. 10.1098/rstb.2003.1428.
A mature forest is in general CO2-neutral. May be the high CO2-concentrations over the Amazone Rain Forest is due to the degradation of the soil after clearing the trees (~10000 km2/year).
The same high CO2 level was also present in the Congo Basin of Africa, Eastern and Southeastern China, The Southeast Asian Peninsula and the islands of Indonesia. These are the most highly vegetative areas of the World (jungles). Maybe past knowledge holds that forests are CO2-neutral but this new satellite mapping possibly suggests otherwise. I would think that more research using OCO-2 data is needed.
Which time of the day was the measurement?
The CO2 level of a CO2 sink would be lower than surrounding non-sink areas except at Dawn if there was a CO2 balance. It would never show a larger CO2 level than the surrounding areas unless there was a CO2 imbalance.
Strange question. Satellite measurements don’t care about day and night. The messure continuously.
Caption:
Average diurnal old-growth forest-atmosphere exchange of CO 2 for May and July of 1998 and 1999, as measured by eddy-covariance at 70 m, and storage measured by a vertical profile system. July 1998 was during El Ni*o-La Ni*a transition associated drought period, in contrast to July 1999 when ample soil moisture was available. The night-time temperatures were higher in 1998 than 1999. Positive values represent a source of CO 2 60 .
In:
Carbon Dioxide Exchange Between an Old-growth Forest and the Atmosphere
August 2004Ecosystems 7(5):513-524
DOI:10.1007/s10021-004-0141-8
The OCO-2 data I reference was not available until after 2014. Why don’t you reply to the OCO-2 data and mapping?
A day has only 24 hours
I commented on oco on October 4, 2015 12:55 pm
I’ll quit beating around the bush. I think that there is enough evidence available from OCO-2 data mapping to call into question the idea that humans are responsible for the increase in the global CO2 level. I think it also undermines the efficacy of the idea that forcing, flux or ocean outgassing plays a significant role. Most of the human used fossil fuel powered vehicles exhaust the heavier-than-air CO2 only one and a half feet above the Earth’s surface. How long does this CO2 remain airborne on average? I doubt that there is a useful measurement of this. What happens to that CO2 once it contacts the Earth’s surface? I would think that the evaluations of the use and effectiveness of heavier than air gasses employed in World War One might shed some light.
A further thought is that the US Army Chemical Warfare experts might be tasked to construct experiments to observe the behavior of CO2 in the situation I mentioned in my previous comment.
Keep on beating the wrong drum Bill, your balance sheet has a deficit.
Bill, if sands from the Gobi desert can reach California and Sahara sand can reach North Europa, the CO2 can be transported all over the world.
Have a look at the Brownian motion:
https://en.wikipedia.org/wiki/Brownian_motion
If lots of CO2 (or chlorine in WWI) are released from a point source, that stays near the ground until mixed in by wind en turbulence, but once mixed in it stays mixed until captured by some tree or the ocean surface.
Aerial photos of WW1 battlefields subjected to gas attacks show small amounts of gas remaining only in low spots such as deep shell craters a few hours after the attack.
Yes, that is what I am saying: chlorine is much heavier than CO2, but still get mixed and diluted with sufficient air speed and turbulence (like around buildings).
Once mixed, both chlorine and CO2 remain mixed, until for CO2 captured biologically (by photosynthesis) or physically (by water)…
No Hans, he didn’t mix up the two. The figure is from Harde (2019) figure 8 and is the result of a simulation.
Then the simulation of Harde is wrong, as the Eemian interglacial was hotter and did yield far less co2 than today.
Were the CO2 measurements based on ice core evaluation? If so, then the level of CO2 at the location of the ice core was lower than the CO2 levels in areas where the climate was more moderate and allowed vegetation growth.
In the (ant)arctic temperature is the limiting factor for plant growth, not co2.
My point is that the CO2 level where the ice cores were taken was significantly less than in warmer parts of the Earth. It is doubtful that an accurate estimate of the CO2 level in warmer areas could be inferred from ice cores taken in areas that were continually frozen.
Yes they can and still do as you can see when comparing Mauna Loa and South Pole current co2 measurements..
The difference in current CO2 levels between near the North Pole (Barrow) and the South Pole today is only a few ppmv averaged over a year. With as main cause human emissions at about 5 ppmv/year, for 90% in the NH, which result in an increase of about 2.5 ppmv/year, which need about 2 years mixing to reach the same level at the South Pole.
In ancient times the “fastest” CO2 changes were 0.02 ppmv/year between glacial and interglacial transitions…
Mapping, using OCO-2 data has shown the two polar regions to have the lowest level of CO2, the oceans and most of the landmass to have the next lowest and heavily forested regions (jungles) near the equator to have the highest levels of CO2.
Chris,
Harde’s graph indeed is the reverse of reality: his simulation is based on one-input-reactor-one-output scheme where the output is proportional to the CO2 height/pressure in the reactor.
In reality, the bulk of the natural fluxes is not proportional to pCO2 in the atmosphere but mainly (seasonal) temperature dependent and bidirectional: inputs get outputs every half year and then reverse next half year. Moreover ocean and vegetation fluxes are opposite to each other (but vegetation wins the contest in the NH). That is the main problem.
The second problem is that Harde calculates the output against zero CO2, while the outlet is not zero, but to the ocean surface (and vegetation) which have already their own pCO2. When in equilibrium for the current average sea surface temperature, the pCO2 in the atmosphere would be around 295 ppmv, thus following the lowest line in figure 8 of Harde…
Frans,
I finally have read the start of the 2019 article by Harde.
As suspected, he indeed used the one-input-swimming-pool-one-output as base for his calculations…
There he calculates the residence time in:
residence time = mass / influx = mass / outflux (2)
When everything is in equilibrium, thus influx = throughput = outfux
So far so good, that indeed is the formula for the residence time, regardless of which is influx or outflux or even if the influx halfway gets an outflux or reverse…
Then he reverses that formula:
outflux = mass / residence time (3)
That you only may do, if and ONLY IF all fluxes are unidirectional which is absolutely not the case for the natural fluxes. Most natural fluxes are bidirectional with as net result zero change when everything is in equilibrium, thus the net influx = net outflux = zero over a year while the residence time still is the same, as residence time is about throughout, whatever the direction of that throughput.
That is the main error of Harde, Salby, Berry… which makes that all their calculations are based on a wrong concept of the natural fluxes…
The second error – again – is that he calculates the outflux for the full CO2 pressure in the atmosphere, while the outflux is in ratio to the CO2 pressure difference between atmosphere and ocean surface… At 295 ppmv in the atmosphere the net CO2 outflux would be zero…
Thus sorry, completely wrong as concept and therefore completely wrong results…
The 2019 article by Harde can be found at:
https://article.sciencepublishinggroup.com/pdf/10.11648.j.earth.20190803.13.pdf