# CO2 and ocean chemistry

by Dr. Daniele Mazza

Oceans cover about 71% of the earth surface, but their influence on climate change is not only due to high heat capacity of water , not only to the ocean’s water circulation, but to a fact which is widely underestimated : the pH (acidity level) of sea-water is substantially alkaline, ranging from 8.0 to 8.7 . This means that the balance between positive and negative ions is reached by accounting for OH,hydroxide ions, in a far larger amount in respect to H+ hydrogen ions.

The pH value higher than 7 allows seawater to dissolve and react huge amounts of CO2 , carbon dioxide, thus affecting the amount of this gas in the atmosphere by absorbing excess of it. To calculate this excess in respect to what would be the true equilibrium value in the air, all of the chemical reactions involved have to be simultaneously computed, accounting for their equilibrium constants, which in turn depend on temperature.

1 – CO2 (gas) + H2O <==> H2CO3* (H2CO3* is the sum of dissolved CO2 and H2CO3)

2 – H2CO3 <==> H+ + HCO3

3 – HCO3 <==> H+ + CO3– –

4 – H2O <==> H+ + OH

5 – Ca++ + CO3– – <==> CaCO3 (calcite)

6 – Ca++ + OH <==> Ca(OH)+

7 – Mg++ + OH <==> Mg(OH)+

Before calculations, let us explore in some more detail mean seawater composition: summing up all the positive charges (Na+, K+, Mg++, Ca++) one obtains 621.1 moles per liter (mmol/L, or moles per cubic meter mol/m3). Carrying out the same operation for negative charges (Cl, SO4– –, Br ) the result is slightly less : 619.2 mmol/L). 1.9 mmol/l are clearly missing ! The seawater must obey , as all other ionic solutions, to electrical neutrality law, so some negative ions have been ruled out: they are indeed HCO3 and to minor extent OH and to far lesser extent CO3– –. All the last three ions are reactive, in respect of atmospheric CO2..

The presence of OH ions (hydroxide ions) is the reason of a pH>7, their concentrations (due to the logarithmic nature of pH scale) is at pH = 8.0 equal to 0.001 mmol/L whilst that of H+ ions is 100 times less. OH ions alone aren’t enough the fill the gap: we need other negative ions, these are mainly HCO3 ions, and also some CO3– – ions.

This fact has an immense consequence on the equilibrium of CO2 between atmosphere and oceans. Actual atmosphere contains around 850 Gt (giga tonn) of carbon (in form of CO2) while the oceans 38000 Gt of carbon, nearly 45 times more.

So when we talk about ppm CO2 in the atmosphere, that only is the top of the iceberg!

CO2 is a reactive gas, it dissolves (like N2 and O2) and later reacts with water itself (N2 and O2 do not) yielding HCO3 and CO3– – . After these reactions are completed still a third takes place (and is quite usually forgotten) : the formation of a solid salt, CaCO3 See reaction No 5 above. This is called in chemistry precipitation. CaCO3 usually has the form of calcite, aragonite, the other polymorph, is slightly more soluble. The seawater is oversaturated in respect of calcite, due to Ca++ ion concentration of 10.6 mmol/L . However this reaction require nucleation and growth of crystals and is usually sluggish (may speed up in the cell of invertebrates).

The destiny of this salt is to eventually sedimentate in the bottom of the sea, (may not reach the bottom, if very deep it can dissociate again in ions due to extreme high pressure and recycle again) . In any case the very end is to remove CO2 from the atmosphere forming limestone.

In textbooks of climate science or oceanography not always all the reaction are carefully accounted for the temperature influence.

Having taught applied chemistry at university level for more then 30 years, I found a simple but important point. When dealing with the above chemical equilibria, in most of the textbook, their equilibrium constant is considered constant, whilst these should vary with temperature.

I wrote some 300 line code in order to solve simultaneously all the above equilibria and to find if the actual level of 410 ppm of CO2 is in equilibrium or not with seawater carbonated ions. If not (and indeed it isn’t) how far are we from equilibrium and how does the system evolve in order to reach it?

Well I’ll try to resume, then if somebody is interested in detail, please e-mail me.

The complete list of considered equilibria is already written above, their equilibrium constants are calculated from Gibbs energy values (data are taken mainly from NIST database or other thermodynamic databases). Remember that K(eq) = exp(- ΔG/RT), R being the gas constants and T the absolute temperature.

1- ΔG = -20302 – T*(-96.25) (Joule/mol/K)

2- ΔG = 7660 – T*(-96.2) (Joule/mol/K)

3- ΔG = 14850 – T*(-148.1) (Joule/mol/K)

4- ΔG = 55836 – T*(-80.66) (Joule/mol/K)

5- ΔG = -13050 – T*(-202.9) (Joule/mol/K)

6- ΔG = -7576 (Joule/mol/K)

7- ΔG = -14656 (Joule/mol/K)

From the above treatment of inorganic carbon chemistry in seawater and the simultaneous resolution of temperature-dependent equilibria, interesting results are obtained. They are presented in graphic form, for sake of simplicity.

Figure 1 shows how CO2 if far more soluble in alkaline waters, like seawater. Compare the red line (ocean water) with blue one (pure water). On x-axis are ppm CO2 in standard air at 17°C (from 200 to 600) and on y-axis the C(T) , total (inorganic) carbon content, i.e. the sum of CO2(aq) , H2CO3 , HCO3 and CO3– – . Note how, increasing ppm CO2 pH changes slightly from 8,72 to 8,27 not so dramatically.

Next figure 2 indicates how temperature affects the inorganic carbon equilibria at constant CO2 (400 ppm). With increasing temperature the DIC or C(T) (total dissolved inorganic carbon) decreases and pH increases.

This explains why CO2 is released in air in warm equatorial waters and absorbed in cold waters.

Figure 3 gives us a comprehensive view of the degree of non-equilibrium in the (average) CO2 exchange between air and ocean. The blue point represents actual 400 ppm value that should reach the 315 ppm equilibrium value with an average sea temperature of 17°C

Ocean water are therefore a huge reservoir for CO2 that waits to be filled.

Up to now calcite precipitation isn’t taken into account. But this is done in figure 4, which explains how CaCO3 forms and thus collects still other huge quantities of CO2. Red curve represents C(T) as a function of temperature with no precipitation of calcite (the same as fig. 1), green line with complete calcite precipitation (We assume C(T) = 1.85 to be a constant value).

The real situation is slowly moving from the red to the green curve, which will be reached at the end. How long does it take? Should be a question of some years or more but the phenomenon will go that way and not the reverse. Blue line is the quantity of limestone at the end of process (green curve). Limestone in geological time will be pushed to subduction by plate tectonic movements, heated by magma and in the far end decomposed to CO2 and calcium silicates. CO2 will be emitted in the volcanoes again in the air after million of years, far enough so that all fossil fuels are burned out !

Conclusions : CO2 is at 410 ppm far above the equilibrium value (315) , provided a standard seawater composition and an average ocean temperature of 17°C (taken from wikipedia). No doubt that solubility will force more CO2 to be stored in oceans . Moreover if we consider CaCO3 formation (seawater has overshot the solubility of this salt nearly 50 times but nucleation and growth are slow) still more CO2 will be stored by limestone.

Daniele Mazza

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May 18, 2019 10:20 pm

“How long does it take? Should be a question of some years or more…”
Yes, that is the question. Currently about half the CO2 we have produced remains in the air, and about half has gone into the sea. But we keep producing more.

Joel O'Bryan
Reply to  Nick Stokes
May 18, 2019 11:35 pm

This is just physical chemistry of CO2 and seawater with oceans as a sink.

The biological sinks are still revving up, catching up as trres respond, growing seasons lengthen, and high latitudes become more productive. As seen in the NH CO2 drawdown by ~6 ppm from the 5 months of May to end-September, the biological sink is far more rapid than the 7 months of increasing CO2 (~8 ppm) of October to end-April.

And all it will take is ~1 week additional growing period tacked onto each end of the drawdown period to completely pull down the CO2 emissions to a net annual null change. And then the biological sinks will still be running long after anthropogenic emissions diminish under fossil fuel consumption due to depletion of resources by the end of the century.

Biology has ruled the carbon cycle drawdown for the last 520 millions years. The Earth has been in near CO2 starvation for the last 2 million years. Mankind is setting that right again for about 10,000 years, when starvation levels may again be approached. But by then we’ll be deep into the glacial, and every bit of CO2 will be cherished by whoever is here then.

4TimesAYear
Reply to  Joel O'Bryan
May 19, 2019 12:55 am

We’re not getting “1 week additional growing period tacked onto each end” though. May snows and killing frosts in the plains states and early snows in October. Saturday had snow in the Dakotas. A few days ago there were frost advisories.

Editor
May 19, 2019 1:28 am

4Times, you don’t understand. If temperature and precipitation fulfill alarmist expectations, it’s totally predictable climate.

But if the changes don’t fulfill alarmist expectations … it’s just weather, nothing to see here, move along …

w.

Reply to  Willis Eschenbach
May 19, 2019 2:34 am

Then there is this:
“The climate system is a coupled non-linear chaotic system, and therefore the long-term prediction of future climate states is not possible. “ https://www.ipcc.ch/ipccreports/tar/wg1/501.htm (IPCC third Assessment Report (2001) Section 14.2.2.2, page 774)

Robert W. Turner
May 19, 2019 11:40 am

It was snowing as far south as the NE-KS state line.

R Shearer
Reply to  Joel O'Bryan
May 19, 2019 7:30 am

Yes, life is key, so easily ignored but is the reason that makes this debate possible. Could it be that mankind was part of Gaia’s plan all along?

TG
Reply to  R Shearer
May 19, 2019 6:43 pm

Absolutely,

donb
Reply to  R Shearer
May 20, 2019 12:23 pm

Nature is a giant experiment into what is possible.

Samuel C Cogar
Reply to  Joel O'Bryan
May 19, 2019 8:54 am

Joel O’Bryan – May 18, 2019 at 11:35 pm

The biological sinks are still revving up, catching up as trres respond, growing seasons lengthen, and high latitudes become more productive. As seen in the NH CO2 drawdown by ~6 ppm from the 5 months of May to end-September, the biological sink is far more rapid than the 7 months of increasing CO2 (~8 ppm) of October to end-April.

Joel O’Bryan, I wish you would educate yourself on the ACTUAL “sinks and sources” for the average ~6 ppm biyearly (seasonal) cycling of atmospheric CO2 ppm quantities …….. as well as the average ~1 to 2 ppm yearly increase in atmospheric CO2 ppm quantities.

Joel, in your above statement you presented two “functions” which are both biological impossibilities.

The first one being that the …… ”the NH CO2 drawdown by ~6 ppm during the 5 months of mid-May to end-September” is a direct result of the ingassing of CO2 by the green-growing biomass. WRONG

What about …… ”the SH CO2 drawdown by ~6 ppm during the 5 WINTER months of mid-May to end-September”? Did the green-growing NH biomass ALSO “suck up” all that ~6 ppm CO2 out of the SH?

And what about …… all that CO2 emissions resulting from the microbial decay/rotting of the dead biomass in the NH during the 7 non-WINTER months of mid-March through October?

“DUH”, microbial decomposition of the dead biomass in the NH always begins 2 to 3 weeks prior to the ingassing of CO2 by the live biomass. And it “begins” in January along the US Gulf Coast and progresses northward to the higher latitudes by mid to late June. (as defined on the PZG map link at the bottom of this post)

And Joel, your second “biological impossibility” is your claim/insinuation that the …… “microbial decomposition of dead biomass in the NH is responsible for the 7 months of increasing atmospheric CO2 ppm (~8 ppm) between October 01 and mid-May of each calendar year.

Joel, …… microbes are “unionized” …… they only engage in “rotting” work when the dead biomass is “wet n’ warm”, ….. but not much at all in the NH Fall and Wintertime iffen the dead biomass is “dry n’ cold/frozen”.

Joel, there is a reason they publish Planting Zone Guides (PZG) such as this one, to wit:

Joel O'Bryan
Reply to  Samuel C Cogar
May 19, 2019 10:24 am

Samuel,
Did I say anything about the SH CO2 dynamics? No.
The SH clearly doesn’t have the seasonal atmospheric CO2 swings the NH does. And the NH Swings increase in amplitude the higher the latitude. The -6/+8 swing I mention is for the MLO record. But NOAA/ESRL Alaskan monitoring sites show more of a -9/+11 ppm CO2 seasonal swing. Clearly the flux rates of the sinks and sources are both daylight and temperature dependent.
The seasonal swings due to biological activity are not seen in SH records. The Southern Ocean is a big steady sink, buffering what is happening there.

So the SH CO2 sinks and sources dynamics are clearly quite different than the NH for a variety of reasons.
– A cold, relatively sterile Antarctic land mass dominating the southern polar area, unlike the polar ocean of the NH.
– The huge difference in relativity productive growing areas between the NH and SH.
– The dominance of the Southern Ocean on primary productivity and that most Southern Ocean sea ice melts every year, unlike the Arctic Ocean.

Did I mention anything about rotting biomass? No.
Nothing you said, contradicts what I said. You are claiming I said things I didn’t. And claiming I “insinuated” something in a short comment post is simply your wanting to read something I didn’t say. That’s a strawman argument.

What I said was based on MLO observation of the CO2 seasonal changes in the NH. The decreasing CO2 May-Sept has a higher absolute rate than the increasing rate Oct-April. The difference between the two is the annual increase.
I said nothing about “microbes rotting”, nor “unionized” biomass in general. Those are all your ideas and words. The NH forests of Northern US, Canada, Europe and Siberia are clearly a major factor in the CO2 drawdown though, that’s something that the SH does not have. Both hemispheres have major primary productivity increases in their oceans though when the sunlight is available for photosynthesis.

Samuel C Cogar
Reply to  Joel O'Bryan
May 19, 2019 3:26 pm

Joel O’Bryan – May 19, 2019 at 10:24 am

The SH clearly doesn’t have the seasonal atmospheric CO2 swings the NH does.

“DUH”, iffen it was being measured at:

Latitude: 19.5362° South
Longitude: 155.5763° West
Elevation: 3397.00 masl (11,145.01 feet above sea level )

Then it would be damn close to what the Mauna Loa measurements are.

And the NH Swings increase in amplitude the higher the latitude. The -6/+8 swing I mention is for the MLO record. But NOAA/ESRL Alaskan monitoring sites show more of a -9/+11 ppm CO2 seasonal swing.

Joel, do you suppose the altitude above sea lever where the CO2 measurements are being made ….. has anything to do with it? ME THINKS SO, ……. to wit:

Barrow Atmospheric Baseline Observatory
Latitude: 71.3230° North
Longitude: 156.6114° West
Elevation: 11.00 masl (36.09 feet above sea level)

Mauna Loa, Hawaii Observatory
Latitude: 19.5362° North
Longitude: 155.5763° West
Elevation: 3397.00 masl (
11,145.01 feet above sea level )

South Pole Observatory (SPO)
Latitude‎: ‎90.00° South
Longitude‎: ‎59° East
Elevation‎: ‎2840 masl (9,317.58 feet above sea level)

The seasonal swings due to biological activity are not seen in SH records.

“DUH”, the seasonal swings due to biological activity are not seen in NH records either …… because the biyearly (seasonal) swing is not the result of biological activity.

Joel, ….. read my writing again, …… the biyearly (seasonal) swing in atmospheric CO2 ppm is a biological impossibility ….. that is attested to and confirmed by the USDA and most every Health Department around the world, to wit, read it and weep:

United States Department of Agriculture Food Safety

Refrigeration slows bacterial growth. They are in the soil, air, water, and the foods we eat. When they have nutrients (food), moisture, and favorable temperatures, they grow rapidly, ….. Bacteria grow most rapidly in the range of temperatures between 40 and 140 °F, the “Danger Zone,” …..
A refrigerator set at 40 °F or below will protect most foods.

http://www.fsis.usda.gov/wps/wcm/connect/934c2c81-2a3d-4d59-b6ce-c238fdd45582/Refrigeration_and_Food_Safety.pdf?MOD=AJPERES

Joel, me thinks you should have a talk with Victoria Henshaw ….. cause me thinks she knows more about …… microbial decomposition of dead biomass …….. than you do, to wit:

Ooooh, that smell! Odors rise with the temperature

Your nose doesn’t lie – odors intensify in the warm summer months, be they of rotting garbage on the sidewalk or fragrant flowers blooming in a garden.

The combination of heat and humidity allows bacteria to grow faster and smells to travel farther, said Victoria Henshaw, who researches urban smells throughout the world.
http://usnews.nbcnews.com/_news/2013/07/17/19524140-ooooh-that-smell-odors-rise-with-the-temperature?lite

Cheers, Sam C

Ps: iffen you are afraid of losing your job ….. then I can understand your refusal to acknowledge specific scientific truths.

Jim Ross
Reply to  Joel O'Bryan
May 19, 2019 11:46 pm

Samual C Cogar,

So, if the “the biyearly (seasonal) swing in atmospheric CO2 ppm is a biological impossibility”, what is the cause of the daily CO2 cycle?

Also, what is the cause of the rapid reduction in surface ocean CO2 seen early April every year at this location (Gulf of Alaska):
https://pmel.noaa.gov/co2/story/GAKOA
Note: plot is slow to display.

Samuel C Cogar
Reply to  Joel O'Bryan
May 20, 2019 4:36 am

Jim Ross – May 19, 2019 at 11:46 pm

Samual C Cogar,

So, if the “the biyearly (seasonal) swing in atmospheric CO2 ppm is a biological impossibility”, what is the cause of the daily CO2 cycle?

Jim Ross, that depends on which “daily” CO2 measurements you are asking about.

Here is the url link to the daily measurements at Mauna Loa …… and they are not biologically driven,

NOAA’s complete weekly/daily average Mona Loa CO2 ppm data
ftp://ftp.cmdl.noaa.gov/ccg/co2/trends/co2_weekly_mlo.txt

But if you are asking about daily CO2 measurements taken at near-surface (ground) locations where there is “green-growing biomass” and/or “decomposing biomass” ……. then there is a good possibility that they are “biologically” driven. (Except of course, in desert areas and active volcanic areas.)

But the aforenoted biological outgassing of CO2 has no effect whatsoever on the Mauna Loa measurements which are drive by Henry’s Law and the seasonal temperature change of the SH ocean waters.

And, …… Jim Ross, …. don’t you be fergettin that “green-growing” biomass ingasses CO2 during photosynthetic activity (daylight) ……. but also outgasses CO2 …… 24-7 as a result of its own metabolism, …. thus the daily CO2 measurements in close proximity to “green-growing” biomass will normally be greater at nighttime ……. and decomposing “dead biomass” on top of or under the surface can/will cause elevated CO2 measurements WHENEVER there is sufficient “moisture and warm temperatures”.

Jim Ross
Reply to  Joel O'Bryan
May 20, 2019 6:06 am

Samuel,

That answers half of my question. Thank you.

How about the CO2 variation at Gakoa?

Samuel C Cogar
Reply to  Joel O'Bryan
May 20, 2019 7:49 am

Jim Ross – May 20, 2019 at 6:06 am

That answers half of my question. Thank you.

How about the CO2 variation at Gakoa?

You mean this ”variation”, ……. Right?

Also, what is the cause of the rapid reduction in surface ocean CO2 seen early April every year at this location (Gulf of Alaska):

Excerpted from cited link:

The GAK 1 time series appear to be a reliable proxy for the freshwater content, and the geostrophic, baroclinic component of the mass and freshwater transport in the Alaska Coastal Current along the Cape Fairfield Line

Jim Ross, ….. I know little to nothing about the “study” you cited, ……. but iffen I t’were to make an edumacated guess it would have to be, to wit: ……

The rapid reduction in surface ocean CO2 seen in early April every year at this location (Gulf of Alaska) is surely the direct result of a horrendous influx of “fresh” meltwater due to the Spring thaw of Alaskan rivers that empty into the Gulf of Alaska.

Like pictured here —- http://www.riskmanagementmonitor.com/wp-content/uploads/2015/03/Ice-flooding1.jpg

Jim Ross
Reply to  Joel O'Bryan
May 22, 2019 12:57 am

Samuel,

The oxygen and salinity data at Gakoa would indicate that the spectacular drop in pCO2 every spring (and the concomitant increase in pH) is much more likely to be due to initiation of photosynthesis by phytoplankton. See also:

https://www.pmel.noaa.gov/co2/story/Iceland

Samuel C Cogar
Reply to  Joel O'Bryan
May 22, 2019 6:43 am

Jim Ross – May 22, 2019 at 12:57 am

The oxygen and salinity data at Gakoa would indicate that the spectacular drop in pCO2 every spring (and the concomitant increase in pH) is much more likely to be due to initiation of photosynthesis by phytoplankton.

Jim, I don’t quite comprehend your claim of a ….. “spectacular drop in pCO2 every spring …… with a concomitant increase in pH” …….. simply because a spectacular drop in CO2 should cause a decrease in carbonic acid …… which should cause a decrease in pH.

Jim, every raindrop that falls is “acidic”, …… carbonic acid, ya know. But not the spring meltwater that flows into the Gulf of Alaska.

[from cited link] “Interannual variations in the partial pressure of CO2 (pCO2) and pH in the North Atlantic reflect environmental changes that affect the marine ecosystem. Quantifying and understanding this variability, particularly in a region where there is vast uptake of anthropogenic CO2 from the atmosphere is critical.

Careful there, Jim, ….. discussing the influx of Gulf of Alaska spring meltwater and citing North Atlantic ocean conditions near Iceland, which is half-a-world away, as a “proof-of-cause” is mighty questionable behavior.

And Jim, ……. just where in the North Atlantic is there environmental conditions that would permit “vast uptake of anthropogenic CO2” …… given the fact that the current crop of Climate Scientists haven’t figured out how to test for the anthropogenic (hybrid) CO2 isotope that contains an H-pyron.

To wit: “The H-pyron or Human-pyron is only attached to and/or can only be detected in anthropogenic CO2 molecules that have been created as a result of human activity. Said H-pyron has a Specific Heat Capacity of one (1) GWC or 1 Global Warming Calorie that is equal to 69 x 10 -37th kJ/kg K or something close to that or maybe farther away.

Jim Ross
Reply to  Joel O'Bryan
May 22, 2019 8:02 am

Samuel,

Have you actually looked at the graphs of these measurements (or the data files)?

At Gakoa on 27 March 2014 the pCO2 of the surface waters was around 400 uatm (same as atmosphere). By 22 April 2014, pCO2 of the surface waters had dropped to below 200. Atmosphere was still around 400. Simultaneously, pH increased from 8.0 to almost 8.4.

I made no comment about the claims in the text of the link. I was referring to the actual observations.

Of course, the link between the Gulf of Alaska and the Iceland Sea is the presence of phytoplankton.

Samuel C Cogar
Reply to  Joel O'Bryan
May 23, 2019 7:29 am

Jim Ross – May 22, 2019 at 8:02 am

Samuel,
Have you actually looked at the graphs of these measurements (or the data files)?

YES I HAVE, ….. now its your turn to look at my data, to wit:

At Gakoa on 27 March 2014 the pCO2 of the surface waters was around 400 uatm (same as atmosphere). By 22 April 2014, pCO2 of the surface waters had dropped to below 200. Atmosphere was still around 400. Simultaneously, pH increased from 8.0 to almost 8.4.

The surface water temperature in the Gulf of Alaska can vary over 10 degrees F from March to May.

And iffen the pCO2 of the surface waters was around 400 uatm in March 2014 ……

And iffen by April 2014 the water temperature had increased over 10 degrees F ……

Then the pCO2 of the surface waters could easily have dropped to below 200 uatm due to the outgassing of its CO2 in accordance with Henry’s Law.

And a 200 uatm outgassing of CO2 from the waters of the Gulf of Alaska would have no measurable effect on the 400 ppm of CO2 situate in the atmosphere above said Gulf.

Remember what I told you, ……… the biyearly temperature “swing” of the VAST ocean surface area of the Southern Hemisphere, …. between the start of Spring and the start of Winter, only creates an average 5-6 ppm difference in atmospheric CO2 ppm quantities, to wit:

Maximum to Minimum yearly CO2 ppm data – 1979 thru 2016
Source: NOAA’s Mauna Loa Monthly Mean CO2 data base
@ ftp://aftp.cmdl.noaa.gov/products/trends/co2/co2_mm_mlo.txt

CO2 “Max” ppm Fiscal Year – mid-May to mid-May

year mth “Max” _ yearly increase ____ mth “Min” ppm
1979 _ 6 _ 339.20 …. + …… __________ 9 … 333.93
1980 _ 5 _ 341.47 …. +2.27 _________ 10 … 336.05
1981 _ 5 _ 343.01 …. +1.54 __________ 9 … 336.92
1982 _ 5 _ 344.67 …. +1.66 __________ 9 … 338.32
1983 _ 5 _ 345.96 …. +1.29 El Niño __ 9 … 340.17
1984 _ 5 _ 347.55 …. +1.59 __________ 9 … 341.35
1985 _ 5 _ 348.92 …. +1.37 _________ 10 … 343.08
1986 _ 5 _ 350.53 …. +1.61 _________ 10 … 344.47
1987 _ 5 _ 352.14 …. +1.61 __________ 9 … 346.52
1988 _ 5 _ 354.18 …. +2.04 __________ 9 … 349.03
1989 _ 5 _ 355.89 …. +1.71 La Nina __ 9 … 350.02
1990 _ 5 _ 357.29 …. +1.40 __________ 9 … 351.28
1991 _ 5 _ 359.09 …. +1.80 __________ 9 … 352.30
1992 _ 5 _ 359.55 …. +0.46 Pinatubo _ 9 … 352.93
1993 _ 5 _ 360.19 …. +0.64 __________ 9 … 354.10
1994 _ 5 _ 361.68 …. +1.49 __________ 9 … 355.63
1995 _ 5 _ 363.77 …. +2.09 _________ 10 … 357.97
1996 _ 5 _ 365.16 …. +1.39 _________ 10 … 359.54
1997 _ 5 _ 366.69 …. +1.53 __________ 9 … 360.31
1998 _ 5 _ 369.49 …. +2.80 El Niño __ 9 … 364.01
1999 _ 4 _ 370.96 …. +1.47 La Nina ___ 9 … 364.94
2000 _ 4 _ 371.82 …. +0.86 La Nina ___ 9 … 366.91
2001 _ 5 _ 373.82 …. +2.00 __________ 9 … 368.16
2002 _ 5 _ 375.65 …. +1.83 _________ 10 … 370.51
2003 _ 5 _ 378.50 …. +2.85 _________ 10 … 373.10
2004 _ 5 _ 380.63 …. +2.13 __________ 9 … 374.11
2005 _ 5 _ 382.47 …. +1.84 __________ 9 … 376.66
2006 _ 5 _ 384.98 …. +2.51 __________ 9 … 378.92
2007 _ 5 _ 386.58 …. +1.60 __________ 9 … 380.90
2008 _ 5 _ 388.50 …. +1.92 La Nina _ 10 … 382.99
2009 _ 5 _ 390.19 …. +1.65 _________ 10 … 384.39
2010 _ 5 _ 393.04 …. +2.85 El Niño __ 9 … 386.83
2011 _ 5 _ 394.21 …. +1.17 La Nina _ 10 … 388.96
2012 _ 5 _ 396.78 …. +2.58 _________ 10 … 391.01
2013 _ 5 _ 399.76 …. +2.98 __________ 9 … 393.51
2014 _ 5 _ 401.88 …. +2.12 __________ 9 … 395.35
2015 _ 5 _ 403.94 …. +2.06 __________ 9 … 397.63
2016 _ 5 _ 407.70 …. +3.76 El Niño __ 9 … 401.03
2017 _ 5 _ 409.69 …. +1.99 ________ 9 … 403.37
2018 _ 5 _ 411.24…. +1.55 ________ 9 … 405.51

The above data is proof-positive of an average 5 to 6 ppm bi-yearly (seasonal) increase/decrease in atmospheric CO2 ….. that DECREASES from mid-May (5) until end of September (9) ….. and then INCREASES until mid-May of the next calendar year.

And, the above data is also proof-positive of an average 2 ppm yearly INCREASE in atmospheric CO2 that is the result of the “warming” of the ocean water from the “cold” of the LIA.

Therefore, as defined by this 2018 Keeling Curve Graph, the “seasonal variation” in atmospheric CO2 is average 5-6 ppm …. and the yearly average increase is 2 ppm, ….. thus the defined 5-6 ppm decrease verses the 7-8 ppm increase.

Note: the “Max” CO2 occurred at mid-May (5) of each year … with the exception of three (3) outliers, one (1) being in June 79’ and the other two (2) being in April 99’ and 2000.

The “Min” CO2 occurred at the very end of September (9) of each year … with the exception of eleven (11) outliers, all of which occurred within the first 7 days of October.

Sam C

Jim Ross
Reply to  Joel O'Bryan
May 24, 2019 3:32 am

Samuel,

“And iffen by April 2014 the water temperature had increased over 10 degrees F ……”

Except that we have SST measurements at Gakoa and the difference between the two dates referenced above (27 March and 22 April 2014) is actually 2.6 degrees F. This is based on the average of 8 measurements on each day, giving 4.3C and 5.7C respectively. According to Henry’s Law, it seems that an increase in water temperature of more like 20C (36 degrees F) would be required to reduce pCO2 by half. Furthermore, the SST at Gakoa continues to increase through to early August, when it reaches 16C but, by this time, the pCO2 has INCREASED back up to 240 μatm, so it is clear that the primary driver of pCO2 variations at this location is not SST.

In addition, O2 in surface waters should also decrease with increased SST (though to a lesser extent than CO2) whereas at Gakoa in April the opposite occurs. The % O2 in the surface water divided by the % O2 of the atmosphere immediately above the ocean surface increases by some 15% between the two dates. Where is this oxygen coming from, if not from initiation of photosynthesis by phytoplankton?

Samuel C Cogar
Reply to  Joel O'Bryan
May 24, 2019 4:23 am

At Gakoa on 27 March 2014 the pCO2 of the surface waters was around 400 uatm (same as atmosphere). By 22 April 2014, pCO2 of the surface waters had dropped to below 200.

Furthermore, the SST at Gakoa continues to increase through to early August, when it reaches 16C but, by this time, the pCO2 has INCREASED back up to 240 μatm, so it is clear that the primary driver of pCO2 variations at this location is not SST.

03-27-14 …… surface water pCO2 = 400 uatm
04-22-14 …… surface water pCO2 = 199- uatm -201
08-13-14 …… surface water pCO2 = 240 uatm +41
08-14-13 thru 03-26-15 …… the surface water pCO2 musta increased 160+ uatm

Except that we have SST measurements at Gakoa and the difference between the two dates referenced above (27 March and 22 April 2014) is actually 2.6 degrees F. This is based on the average of 8 measurements on each day, giving 4.3C and 5.7C respectively.

The % O2 in the surface water divided by the % O2 of the atmosphere immediately above the ocean surface increases by some 15% between the two dates.

1st it is “actually 2.6 degrees F” …….. and then it is “4.3C and 5.7C respectively

And then you divide “percent” by a ”percent” to get a “percent”.

IMPRESSIVE.

Whatevah ya say, Jim, …….. whhatevah ya say

Jim Ross
Reply to  Joel O'Bryan
May 24, 2019 10:29 am

1st it is “actually 2.6 degrees F” …….. and then it is “4.3C and 5.7C respectively”

I am sorry – I didn’t realise your scientific expertise did not extend to dealing in both Fahrenheit and Centigrade. The data is of course in Centigrade, but since you were referring to “over 10 degrees F”, I took the trouble of converting it for you.

First, I said the DIFFERENCE between the two dates … is actually 2.6 degrees F, so that you could compare the actual measurements with your “over 10 degrees F”. Second, 4.3C (27 March, average of 8 measurements) is 39.7F and 5.7C (27 April, average of 8 measurements) is 42.3F. Third, and this is the really tricky bit, 42.3F minus 39.7F is 2.6F.

Samuel C Cogar
Reply to  Joel O'Bryan
May 25, 2019 4:42 am

GISS data show global average temperatures in 2017 rose 1.62 degrees Fahrenheit (0.9 degrees Celsius)

That would put the planet’s average surface temperature in 2017 at 58.62 F (14.9 C).
https://www.space.com/17816-earth-temperature.html

So, the 2017 average surface temp was 58.62 F (14.9 C)

And a 2017 Death Valley high temp was 120 F (48.9 C)

And a 2017 Antarctica low temp was -120 F (-84.4 C)

Death Valley 120 F cancels out the Antarctica -120 F, resulting with 0.0 F (-17.8 C) temp

So that means it was freezing at the Equator, …………. Right

Drake
Reply to  Joel O'Bryan
May 19, 2019 2:04 pm

Duck Creek Utah, has been snowing off and on all day. 2 inches on my deck. 29 degrees F now at 3:00 pm. We are at 8600 feet but have not had this much snow in May in the 12 years I have been coming here. Old timers have spoken of snow on July 4th 35 years ago. Looks like that CYCLE is coming back.

BTW, supposed to snow for the next 2 to 3 days, daytime highs in the high 30s, lows in the middle to low 20s.

beng135
Reply to  Joel O'Bryan
May 21, 2019 9:05 am

Mankind is setting that right again for about 10,000 years, when starvation levels may again be approached.

Yes. The next REAL major extinction event will be CO2 starvation if we humans don’t do something about it. Volcanic activity has diminished to the point of not replenishing the CO2 like it once did.

Reply to  Joel O'Bryan
May 22, 2019 8:43 pm

We may not need any extra time added or extended to the growing season if farmers adapt agricultural methods to enhance top soil organic matter retention during the current growing season that is available. Freeman Dyson explained the idea of an agricultural carbon sink in an honorary lecture he was invited to give in Boston in the 1990’s entitled Heretical Ideas (I forget the exact title) in which he dismissed the threat of AGW/CC based on the predictive value of GCM’s employing fluid dynamical physical principles alone, because they don’t take cloud formation and biological effects into account, and the idiotic assumption that society will not adapt to a threat should it emerge. He didn’t think increased CO2 levels were threat. His working premise based on calculations was that a relatively small increase in topsoil added per year in inches to land now being farmed would zero out the net increase in atmospheric CO2 levels emitted by the burning of fossil fuels. His lecture on Heretical Ideas (and his cry for the need for heretics in science) was posted here on WUWT. Most enjoyable and educational.

Jim Ross
Reply to  Nick Stokes
May 19, 2019 1:31 am

Nick,

What is your source for “about half has gone into the sea”?

According to Global Carbon Budget, the averages since 1959 are about 30% into the terrestrial biosphere, 24% into the oceans and 45% being the airborne fraction (these figures include the highly uncertain estimates for land-use emissions). The airborne fraction (the amount of estimated total emissions not taken up by land and ocean) varies annually by large amounts (especially the estimated land uptake) and ranges between 20% (major eruption) and 80% (major El Niño).

Source and references: https://www.icos-cp.eu/GCP/2018

Reply to  Jim Ross
May 19, 2019 1:56 am

Jim,
My quote was based on the 45% airborne fraction that you quote, assuming that the rest goes into the sea. I may be wrong on that. The source you quote says about half to land sinks, half to sea. That would mean sea uptake is slower. However, there is a bit of an accounting ambiguity. That budget also allows a land use source, which is a significant fraction of the land sink. If you look at net land sink, it is smaller.

Editor
Reply to  Nick Stokes
May 19, 2019 4:43 am

If you convert the total CO2 emissions from GtC to ppm CO2, it works out to about 4 ppm/yr… About twice the rate at which atmospheric CO2 is rising.

The airborne fraction is just a mass balance calculation. Even if we don’t know what the natural flux is, our contribution is a fairly trivial calculation.

Reply to  David Middleton
May 19, 2019 6:28 am

“Even if we don’t know what the natural flux is, our contribution is a fairly trivial calculation.”
It is. But not as shown in the graph. The early rise from about 1800 isn’t “natural”. It is a consequence of land use change; mainly agricultural clearing in the New World. In fact all the increase is man-made. There is a proper calculation and graph taking this into account here.

Editor
Reply to  Nick Stokes
May 19, 2019 6:57 am

Without knowing the true range of the natural flux, that can’t be concluded… Although it is certainly a possibility.

Sheri
Reply to  Nick Stokes
May 19, 2019 2:34 am

And what is happening now is what will always happen, Nick, because ONLY what is happening now is real and it can never change. Yes, we know that. We understand stasis and trend line permanence and all the other false “science” preached. If it’s not happening now, it cannot and will not EVER happen or change. The fundamental law of climate change, that there NEVER be any change.

F1nn
Reply to  Nick Stokes
May 19, 2019 6:21 am

What if the reason to this CO2 problem is sea itself? I have read that there are different time scales for outgassing. Longest was some 800ish years. That takes us to MWP, which warm is now outgassing.

Clyde Spencer
Reply to  Nick Stokes
May 19, 2019 10:30 am

Stokes,
You state the correlation between anthropogenic CO2 release and atmospheric concentration as a causative fact. An alternative hypothesis to consider is that the warming of the oceans is resulting in outgassing, (confirmed by the OCO-2 satellite) which would result in the same level of atmospheric increase, even in the absence of anthropogenic CO2. That is, the correlation is possibly spurious. One can appeal to carbon isotope ratios, but what apparently isn’t taken into consideration is the fractionation of carbon isotopes by photosynthesis, and selective outgassing for the lighter CO2 molecules.

Editor
Reply to  Clyde Spencer
May 19, 2019 10:50 am

Clyde Spencer May 19, 2019 at 10:30 am

Stokes,
You state the correlation between anthropogenic CO2 release and atmospheric concentration as a causative fact. An alternative hypothesis to consider is that the warming of the oceans is resulting in outgassing, (confirmed by the OCO-2 satellite) which would result in the same level of atmospheric increase, even in the absence of anthropogenic CO2.

While you are correct in direction, the problem is in degree. Yes, as you point out, CO2 does go up and down with ocean temperature … but not much.

For example, during the ice ages the global temperature dropped by on the order of three to five degrees.

CO2, of course, went down correspondingly. During glacial periods it averaged about two hundred ppmv, and during interglacials it averaged about two hundred fifty ppmv. Here’s the Vostok record.

This gives us the CO2/temperature relationship, which turns out to be a change of about fifty ppmv per three-degree temperature change, or say seventeen ppmv per degree.

Now, since pre-industrial times CO2 has gone up from about 275 ppmv to 400+ ppmv. That’s about 125 ppmv or so.

And to get this change in atmospheric CO2 from a global temperature change, the globe would have to warm on the order of seven degrees or so … not happening …

So no, it’s not possible that the atmospheric increase in CO2 is a result of oceanic warming.

Best to you,

w.

Clyde Spencer
Reply to  Willis Eschenbach
May 19, 2019 5:34 pm

Willis,
Thank you for your reply. When I look at your graphs, I get a range of approximately 25 PPMV per degree of temperature change for the last 500,000 years of ice core data, instead of your 17 PPMV. But the orders of magnitude are the same.

Those ratios neither explain the rise in temperature (one deg C per 130 PPMV) if CO2 is driving temperature, nor the 130 PPMV if if temperature is driving CO2 outgassing. That is to say, if CO2 is the main driver, temperature should have increased ~ 5-8 deg C. Clearly something is being missed. The things that come to mind are non-linearity in the response, and related to that, much more water vapor in the atmosphere driving the temperature increase once the average temperature gets well above freezing.

I’m afraid the science isn’t settled.

Jim Ross
Reply to  Clyde Spencer
May 19, 2019 11:17 pm

Clyde,

Agreed. The last El Niño was a short-lived “blip” of circa 0.5C and yet it apparently increased atmospheric CO2 by 2ppmv. Background rate was unchanged at 2ppmv/yr before and after.

Plot was generated by NOAA with additional annotations added by myself.

Reply to  Clyde Spencer
May 20, 2019 12:30 am

“it apparently increased atmospheric CO2 by 2ppmv”
That is even way lower than Willis’ rate of 17 ppmv per degree. It is 4 ppm/°. And as he says, nothing in the temperature record, on those ratios, could cause an increase of over 120 ppmv.

Jim Ross
Reply to  Willis Eschenbach
May 20, 2019 1:21 am

Nick,

Did you actually look at the graph? Do you not understand the difference between a short-term temperature “blip” and a longer-term change in atmospheric CO2?

Reply to  Jim Ross
May 20, 2019 2:07 am

Jim,
Yes, I did. But they are your figures. Why did you quote them if not to show the effect of temperature on CO2?

Jim Ross
Reply to  Jim Ross
May 20, 2019 5:59 am

The plot does indeed show an effect of temperature on atmospheric CO2, and hence provides some context, but I didn’t expect anyone to fail to recognise the difference between a “blip” and a long term trend.

Reply to  Willis Eschenbach
May 20, 2019 7:22 am

Willis wrote, “…to get this change in atmospheric CO2 from a global temperature change, the globe would have to warm on the order of seven degrees or so … not happening …
So no, it’s not possible that the atmospheric increase in CO2 is a result of oceanic warming.”

I agree, Willis. We’ve all seen this graph, or similar ones:

If you compare the CO2 and Temperature scales you can see that it shows about 90 ppmv difference between glacial maxima and interglacials, and it shows about eventual 8-10 ppmv CO2 change per °C of warming, in the long term (near the poles, from ice core data).

Of course, since temperature at the poles varies more than elsewhere, the global average temperature change is thought to have been only perhaps half the polar change (though that seems to hold only in the northern hemisphere, currently). So that gets us almost exactly to your estimate of 17 ppmv per °C of warming.

That means to cause 130 ppmv of CO2 increase by that mechanism would require 7-8°C of globally averaged warming.

But that’s at approximate equilibrium, after thousands of years.

95 ppmv of that CO2 increase was in just the last sixty years!

From paleoclimate reconstructions from ice cores, reversals in CO2 trend generally lag reversals in temperature changes by hundreds of years (200 to 1000 years). If it takes, on average, 500 years for a reversal in the direction of the temperature trend to be reflected by a reversal in atmospheric CO2 level trend, that tells us that sixty years is way, way short of enough time to approach equilibrium.

In just sixty years, I very much doubt you’d see even 1/3 of the equilibrium increase, but let’s assume 1/3, to be generous. So to get 95 ppmv of CO2 from warming would require at least 95 / (17/3) = almost 17 °C of warming, in just sixty years.

I hope it is obvious to everyone that Willis is right: ocean warming cannot have caused the measured CO2 increase.

Bob Weber
Reply to  Willis Eschenbach
May 20, 2019 2:47 pm

This gives us the CO2/temperature relationship, which turns out to be a change of about fifty ppmv per three-degree temperature change, or say seventeen ppmv per degree.

Willis it’s not as simple as in how you arrived at 17ppmv/degree.

Take notice at what 60 years of monthly Mauna Loa vs HadSST3 data tells us about the CO2-ocean temperature dependence.

Using the data for the slopes of two of the largest changes in both, in 1988 and 1998, I calculated a rough average CO2-sensitivity to SST3 of deltaCO2/deltaSST3 of 4.5 +-0.3 ppmv/C, about 25% of your value.

I’m sure a more refined analysis would narrow it down a bit better than that.

Why would this be so much lower instead of your value is the real question.

As to the general presumption as to larger portion of atmospheric CO2 is owed to man, I seriously questioned it. I used an estimated burnt fuel portion of the estimated total man-made portion which includes cement production, etc. over the same period to annual Mauna Loa data to find a 0.01 direct correlation for burnt fuels, and a more surprising 0.28 correlation to non-fuel man-made CO2 production compared to the about 0.8 lagged 10-12 months correlation of 12moCO2change to HadSST3.

This tells us the ocean is by far the dominant source of atmospheric CO2, followed by a distant second place non-fuel related man-made CO2 production, so therefore I have to disagree with you on your point.

Bob Weber
Reply to  Bob Weber
May 20, 2019 5:01 pm

I want to clarify mistakes I made. The second plot with the spreadsheet actually has two scales, the ppmv for CO2 change, and Gt for the total and burnt fuel CO2 estimates. The point there is no little correlation wrt annual changes. Secondly, the 0.28 direct correlation is for the total amount, including burnt fuels.

The absolute fraction of man-made vs natural CO2 is a few calculations away. I used Trenberth’s estimated mass of the dry atmosphere at 5.132(10^18)kg and from there the computed CO2 mass is roughly 3(10^15)kg. The last quarter increase to the present amount of atmospheric CO2, just over 400ppm, for an approximate 100ppmv change, equals 7.5(10^14)kg CO2. This when compared to NASA’s estimated 5.5Gt/yr from carbon cycle budget (a sketchy claim), to find it would take at least 409 years for man-made emissions to reach the amount equal to the 100ppmv in that time at that level, so NASA’s estimate is way off.

Bob Weber
Reply to  Bob Weber
May 20, 2019 6:07 pm

so NASA’s estimate is way off.

Qualifying: that’s only if we are to assume, as they do, that the majority of atmospheric CO2 is man-made, which still makes those numbers sketchy as they don’t add up.

OR if the natural portion greatly overwhelms the man-made part, which is what my conclusion has to be, otherwise their numbers would mean Henry’s Law didn’t produce a net atmospheric CO2 gain sometime after man-made emissions started, even after 150+ years of ocean warming, which is what is indicated in NASA’s carbon cycle budget, where the ocean is depicted now as having a small net negative annual contribution after outgassing.

This means we have a decision to make, do we believe as NASA must according to their numbers, that in spite of the rise in ocean temperature since the early 1800s ocean outgassing went net negative, which to me this is a direct violation of Henry’s Law, or do we realize the natural portion has always greatly overwhelmed the man-made part and the warmists’ CO2 ideas are flawed. That’s where I’m at: NASA’s carbon budgeting has led to creative accounting that hides the ocean’s dominate CO2 production role.

Reply to  Bob Weber
May 21, 2019 7:05 am

Bob Weber wrote, “Using the data for the slopes of two of the largest changes in both, in 1988 and 1998, I calculated a rough average CO2-sensitivity to SST3 of deltaCO2/deltaSST3 of 4.5 +-0.3 ppmv/C, about 25% of your value. …
Why would this be so much lower instead of your value is the real question.”

That’s an easy question to answer. Your result is actually consistent with Willis’s result. Willis (and I) estimated the effect of temperature on CO2 from ice cores, with 100,000 year cycles. That’s a near-equilibrium response, after thousands of years. You’re reporting a transient response, which obviously should be much smaller. 25% sounds perfectly reasonable, perhaps even a bit higher than I would have guessed.

Bob wrote, ” I used an estimated burnt fuel portion of the estimated total man-made portion which includes cement production, etc. over …
This tells us the ocean is by far the dominant source of atmospheric CO2, followed by a distant second place non-fuel related man-made CO2 production…”

Something seems to be wrong with your arithmetic. You show burnt fuel accounting for only 50% of manmade (“MM”) emissions in 2013, but the data file you cite shows 94.3%.

Bob continued (in the next comment), “…when compared to NASA’s estimated 5.5Gt/yr from carbon cycle budget…”

I don’t know what that means. Anthropogenic CO2 emissions are approaching 40 Gt/year. I think the last estimate I saw was 37 Gt/yr. (Note that the data file you cite is showing quantities of carbon, not CO2, so you have to multiply by (44/12) to get CO2 mass.)

Bob continued, “…it would take at least 409 years for man-made emissions to reach the amount equal to the 100ppmv in that time at that level…”

8 Gt CO2 = 1 ppmv, so 100 ppmv is 800 Gt. At 37 Gt/year that’s 22 years, not 409. (But, of course, emissions haven’t been at 37 Gt/yr for 22 years, and negative feedbacks are removing a lot of CO2 from the atmosphere.)

Bob continued (in the 3rd comment), “…that’s only if we are to assume, as they do, that the majority of atmospheric CO2 is man-made…”

That’s not the assumption. Manmade CO2 emissions have raised the atmospheric CO2 concentration by just under 50%. However, because much of that “fossil” CO2 has been exchanged with other carbon reservoirs (ocean, biosphere), the percentage of anthropogenic CO2 in the atmosphere is much lower than that.

Bob Weber
Reply to  Bob Weber
May 21, 2019 5:00 pm

Thanx for taking the time Dave Burton. I’ll go point by point as you did.

1) The estimated CO2 conc. change from 1850-2013 was about 112ppm, and for the HadSST3 record that started in 1850, using annual data, the change was 0.691C, for a sensitivity factor of 162ppm/C, 36X the transient response I calculated before using monthly data, and 9.5X yours and Willis’ value. So right there I question the usefulness of doing longer-term calculations to get at an appropriate sensitivity factor.

2) Yes I did make an arithmetic error by not including the ‘solid’ fuel in the burnt total – my bad (now I know how Willis feels when stuff like that happens for him). The corrected correlation for burnt fuels improved to 0.25 – no wonder I was surprised.

3) I got the 5.5Gt/yr flux for burnt fuels from NASA’s carbon budget graphic. I did incorporate the 3.67 (44/12) ratio for CO2 mass in my calculations.

4) The 409 years is another mistake, off by one decimal. It’s 40.9 years. Ouch, that one burns it was so stupid. That is a much faster accumulation than the time it took for the additional 100ppm to accumulate to today’s level, about 143 years from 1870-2013.

5) Manmade CO2 emissions have raised the atmospheric CO2 concentration by just under 50% I don’t agree with that right now. The total CO2 from burnt fuels from 1870-2013 (the approx. time of the 100ppm change) produced 6.1X more CO2 than the net 100ppm atmospheric accumulation in that time.

The last calculation means the ocean had to sink 5.1X the amount left in the atmosphere of just the man-made portion. I still think the man-made portion is much overstated, as it leaves no room for a positive net gain from outgassing via Henry’s Law during a net positive temperature rise, a violation of physical law, imo. I’m not sure how you arrived at 50% man-made still in the atmosphere, as that would imply 50% from other sources including outgassing still remain, and the mm CO2 uptake would be much larger than what my 12moCO2change indicates really happens, so to me your 50% is way too high. As I said before, it’s not adding up, even after the corrections.

Dave I want to thank you again for walking through it. I attribute my math errors to rushing to meet the AGU abstract deadline on May 8, which I ended up pulling anyway. My solar work was much easier to sort out, and I took a few years to develop and check my work.

Reply to  Bob Weber
May 23, 2019 7:28 am

Bob Weber wrote, “1) The estimated CO2 conc. change from 1850-2013 was about 112ppm, and for the HadSST3 record that started in 1850, using annual data, the change was 0.691C, for a sensitivity factor of 162ppm/C, 36X the transient response I calculated before using monthly data, and 9.5X yours and Willis’ value.”

That’s because those CO2 level increases were due to temperature changes, and this much larger CO2 level increase was due to direct additions of CO2 to the atmosphere, from burning fossil fuels and manufacturing cement.

Bob continued, “3) I got the 5.5Gt/yr flux for burnt fuels from NASA’s carbon budget graphic. I did incorporate the 3.67 (44/12) ratio for CO2 mass in my calculations.”

Interesting! That slide is from this 2011 presentation:
https://slideplayer.com/slide/5117097/

The label beside it says “Fossil Fuels & Cement Production,” but it’s in a different color, so perhaps they meant just fossil fuels.

Even so, their “5.5” figure was way out of date, even back in 2011.

If they meant to include cement production, that “5.5” figure would have been correct back in about 1986.

If they meant fossil fuels, alone, then that “5.5” figure would have been correct back in about 1987.

Clearly, it’s just another mistake by the folks at NASA.

Bob continued, “5) Manmade CO2 emissions have raised the atmospheric CO2 concentration by just under 50% I don’t agree with that right now. The total CO2 from burnt fuels from 1870-2013 (the approx. time of the 100ppm change) produced 6.1X more CO2 than the net 100ppm atmospheric accumulation in that time.”

There appears to be another arithmetic error in there, somewhere, or perhaps a typo (“6.1” for “1.6”).

https://sealevel.info/global.1751_2014.ems3.xlsx

That sum is 378.70 GtC =
‍‍‍‍‍‍ ‍‍ × (44/12) = 1388.56 Gt CO2 =
‍‍‍‍‍‍ ‍‍ ÷ 8.053 Gt/ppmv = 172.4 ppmv

So fossil fuels emitted 1.6× more CO2 than the measured 108 ppmv atmospheric increase from 1870 (288 ppmv) to 2013 (396.5 ppmv), rather than 6.1×.

Jim Ross
Reply to  Clyde Spencer
May 19, 2019 12:51 pm

I don’t want to go off on a tangent here, but why do you say that fractionation is not taken into account? It seems to me that it is (to the extent that it appears to be poorly understood at the sea-air boundary). The problem is that even Ralph Keeling cannot match the δ13C observations despite it following a very simple relationship. All additional CO2 since 1750 has had a δ13C of -13 per mil (on average). Show me a model that explains that.

Clyde Spencer
Reply to  Jim Ross
May 19, 2019 8:45 pm

Jim Ross,
My understanding is that the claim is commonly made that the increase in atmospheric CO2 is the result of the burning of fossil fuels because of an increase in the relative proportion of C12, resulting from the preferential selection of C12 over C13 by photosynthetic plants. But, to the extent that the net change might be the result of outgassing, one should expect the lighter isotope (C12) to escape more easily, qualitatively changing the carbon isotope ratio in the same direction as burning C12-rich fossil fuels.

Jim Ross
Reply to  Clyde Spencer
May 20, 2019 1:03 am

Clyde,

Thanks very much for your response. I think that fractionation was either ignored or seriously underestimated until relatively recently, but is now incorporated in the models (for what it’s worth). You are also correct regarding the direction of the effect. NOAA’s estimate for CO2 flux into the atmosphere from ocean outgassing is -9.5 per mil.

We were told many times over in the past that ocean outgassing would increase the atmospheric δ13C and hence could not be the cause of the decline in the isotopic ratio. That simplisitic argument seems to be dead now, given that -9.5 per mil is lower that the atmospheric level (now about -8.5 per mil). In any event, as I noted above, the decline in atmopsheric δ13C reflects, on average, a δ13C of the incremental CO2 of -13 permil, a bit lower than the ocean-air flux estimate, but much higher than the terrestrial biosphere or fossil fuels (-26 and -28 per mil, respectively).

For me, the most interesting aspect of the δ13C decline is the fact that it seems to be have been pretty much constant value for the isotopic content of the extra CO2 (-13 per mil, other than short term variations related to ENSO) since the start of CO2 growth.

Charles Higley
Reply to  Nick Stokes
May 19, 2019 3:20 pm

The half life of CO2 in the atmosphere is about 5 years, which means it is quite dynamic. Our increasing emissions are having no influence on the steady rate of atmospheric CO2, no effect, so it’s not us.

Any policy based on decreasing CO2 emissions is patently wrong, as we need more CO2 not less, to keep up our food supply while the planet continues to cool. CO2 IS PLANT FOOD!

Earth is a soda as far as CO2 is concerned. When there is warming, the oceans slowly warm a bit and start to outgas CO2. There is clearly a lag period at all time scales. When there is cooling, it takes time for the oceans, again to adjust and take up CO2 more slowly than it was outgassed, as it is only absorbed passively at the water surface, while outgassing is more active and rapid.

The chemistry presented above is good regarding the extended equilibrium system for CO2 but the impetus for the paper being some worries about CO2 warming the planet is wrong. There are also other buffer systems in play that put the brakes on changes in ocean pH.

No gas at any concentration in the atmosphere can warm the climate. With the water cycle and convection, the global heat engine is just too powerful.

Reply to  Charles Higley
May 20, 2019 10:34 am

Charles Higley wrote, “The half life of CO2 in the atmosphere is about 5 years…”

No, it is much longer than that.

This is a (log scale) plot of the decay of 14C in the atmosphere, following the 14C “bomb spike.”

http://2.bp.blogspot.com/-G79oXdgIZC4/UnteTCVaGGI/AAAAAAAAAA0/AbSzY3s5ZP0/s1600/logc14.jpg

When atmospheric tests of A-bombs and H-bombs suddenly ceased (following the atmospheric test ban treaty), the 14C concentration fell on a near-perfect exponential decay curve, with a half-life of 11.5 years, implying a residence time of 16.6 years.

(Note: 14CO2 is 4.5% heavier than normal 12CO2, which affects biological uptake and diffusion rates slightly. But not much.)

Some of the processes which remove 14CO2 from the atmosphere do so by exchanging it for 12CO2. Those processes cause the fraction of 14C in the atmosphere to decline without actually reducing the amount of CO2 in the atmosphere. That means the 11.5 year half-life and 16.6 year residence time are necessarily less than the effective lifetime of CO2 emissions.

The effective lifetime of anthropogenic additions to CO2 in the atmosphere, variously defined as the time it would take for 2/3 or 63% (1-(1/e)) is roughly fifty years, making the half-life about 35 years.

That’s the result that Prof. Richard Lindzen reported during the Q&A (3rd video) of this (excellent!!!) lecture:
● Part 1: https://www.youtube.com/watch?v=hRAzbfqydoY
● Part 2: https://www.youtube.com/watch?v=V-vIhTNqKCw
● The Q&A which followed: https://www.youtube.com/watch?v=69kmPGDh1Gs (including his discussion of CO2 atmospheric lifetime)

That’s also the approximate result that Dr. Roy Spencer found:
http://www.drroyspencer.com/2019/04/a-simple-model-of-the-atmospheric-co2-budget/

That’s also the approximate result that I got, first with a little program to simulate declining CO2 levels, based on the historical CO2 removal rate as a function of CO2 level, and then with a modified version of the program based on Dr. Spencer’s model; source code here:
http://sealevel.info/CO2_Residence_Times/

Ferdinand Engelbeen reported roughly the same result, here:

That last one is a link to Ferdinand’s comment on a blog article by Ed Berry, in which Ed claims that the residence time of anthropogenic CO2 is very short, mankind’s CO2 emissions have little effect on the CO2 level, and the rise in atmospheric CO2 level is due to a warming climate. (Ferdinand is right, and Ed is wrong.)

What this means is that if anthropogenic CO2 emissions suddenly ceased, it would take about 30-40 years before half of the cumulative anthropogenic CO2 increase was gone from the atmosphere.

Reply to  Dave Burton
May 20, 2019 1:52 pm

Correction (I left out a phrase):

I wrote:

“…variously defined as the time it would take for 2/3 or 63% (1-(1/e)) is roughly fifty years…”

But I intended:

“…variously defined as the time it would take for 2/3 or 63% (1-(1/e)) of the anthropogenic CO2 to be removed if emissions ceased is roughly fifty years…”

Howard Dewhirst
May 18, 2019 10:30 pm

I’d like to ask Daniele why it is that no matter how much human CO2 emissions grow we are told that roughly half is sequestered by natural processes (including photosynthesis) – or is the apparently steady % of sequestration due to the massive size of the full carbon cycle, so that it would need a much larger increase for us to detect a change in the rate of sequestration?

markx
Reply to  Howard Dewhirst
May 19, 2019 2:42 am

I too find this puzzling…. of the entirety of the annual flux of CO2, each year the planet somehow deals with 98.5% of it, leaving 1.5% to accumulate in the atmosphere. (as we know, the blame being allocated to the anthropogenic emissions which are are about 3% of that flux, and are apparently partly absorbed, leaving this 1.5% excess).

There must be VERY precise processes at work if they can deal with a 1.5% excess, but not a 3% excess.

Makes me wonder if we have the ‘mechanism of airborne CO2 stability wrong. Or cause and effects confounded.

Kaiser Derden
May 19, 2019 4:49 am

there is obviously a very precise process involved … and clearly a complicated one … and currently the complete components of this process are not being explored by climate scientists … but “the science is settled” so … never mind …

Editor
Reply to  Howard Dewhirst
May 19, 2019 4:47 am

It appears to be fairly constant, at least over the past 50 years or so… Which is odd.

Prior to 1960, atmospheric CO2 was actually rising faster than emissions.

From about 1940 through 1955, approximately 24 billion tons of carbon went straight from the exhaust pipes into the oceans and/or biosphere.

The stabilization of atmospheric CO2 concentration during the 1940s and 1950s is a notable feature in the ice core record. The new high density measurements confirm this result and show that CO2 concentrations stabilized at 310–312 ppm from ~1940–1955. The CH4 and N2O growth rates also decreased during this period, although the N2O variation is comparable to the measurement uncertainty. Smoothing due to enclosure of air in the ice (about 10 years at DE08) removes high frequency variations from the record, so the true atmospheric variation may have been larger than represented in the ice core air record. Even a decrease in the atmospheric CO2 concentration during the mid-1940s is consistent with the Law Dome record and the air enclosure smoothing, suggesting a large additional sink of ~3.0 PgC yr-1 [Trudinger et al., 2002a]. The d13CO2 record during this time suggests that this additional sink was mostly oceanic and not caused by lower fossil emissions or the terrestrial biosphere [Etheridge et al., 1996; Trudinger et al., 2002a]. The processes that could cause this response are still unknown.

[11] The CO2 stabilization occurred during a shift from persistent El Niño to La Niña conditions [Allan and D’Arrigo, 1999]. This coincided with a warm-cool phase change of the Pacific Decadal Oscillation [Mantua et al., 1997], cooling temperatures [Moberg et al., 2005] and progressively weakening North Atlantic thermohaline circulation [Latif et al., 2004]. The combined effect of these factors on the trace gas budgets is not presently well understood. They may be significant for the atmospheric CO2 concentration if fluxes in areas of carbon uptake, such as the North Pacific Ocean, are enhanced, or if efflux from the tropics is suppressed.

MacFarling-Meure, C., D. Etheridge, C. Trudinger, P. Steele, R. Langenfelds, T. van Ommen, A. Smith, and J. Elkins (2006), Law Dome CO2, CH4 and N2O ice core records extended to 2000 years BPGeophys. Res. Lett., 33, L14810, doi:10.1029/2006GL026152.

Reply to  Howard Dewhirst
May 19, 2019 6:20 am

“roughly half is sequestered by natural processes”

There is a rather subtle mathematical reason for the apparent constancy, explained here. It is a consequence of the fact that the rise in CO2 ppm has been close to exponential (offestting the long-term constant of about 280 ppm). If you assume that there is any impulse response governing the timing, of any shape, a constant ratio results.

R Shearer
Reply to  Nick Stokes
May 19, 2019 7:36 am

There is no long-term constant as far as atmospheric CO2 is concerned though smoothing by ice-cores makes it appear that CO2 concentration is more stable than it actually is.

Ian W
Reply to  R Shearer
May 26, 2019 3:37 am

It seems to be assumptions all the way down

May 18, 2019 11:47 pm

I have to say that I don’t understand it, but its interesting.

But getting back to the Global warming nonsense, what does it tell us.
We are told that via the Logetherimic law. that its the first 150 pip that
does all the work of creating the Greenhouse effect, hence the present
figure, or any subsequent increase will make no difference.

Does this interesting chemical process finding change that ?

MJE VK5ELL

michael hart
May 18, 2019 11:49 pm

“In textbooks of climate science or oceanography not always all the reaction are carefully accounted for the temperature influence.”

Indeed. Which makes using an average ocean temperatrure seem like an oversimplification. Some areas will be thermal sources of CO2 and others will be sinks. Also the Gibbs free energy is a function at constant pressure, but you do note the added complexities of the enormous pressure variations in the oceans.

Rod Evans
Reply to  michael hart
May 19, 2019 2:05 am

Michael, I am simply an observer of the data, I am not an expert, but from the above study, it states the average ocean temp is taken as 17 deg C. The thermal sources of CO2 you mention, will be countered by the sinks so the observed gap, between seawater CO2 equilibrium and actuality as shown in the graph, is valid.
Also, is suggests, the current 410 ppm CO2 in the atmosphere, will be drawn down to around the 315 ppm level over time. There is nothing to prevent the reaction. The oceans can never warm sufficiently to maintain/drive the atmospheric CO2 level above a point it has already been, in Earth’s history. It is also true to state, there is nowhere near enough CO2 in the atmosphere to acidify the oceans even if all atmospheric CO2 was able to be taken up, which is impossible.
With that being the situation, and with global temperature at a very low level compared with past periods going back hundreds of millions of years, I for one, am completely relaxed about our usage of fossil fuels that increase prosperity and increase CO2. I would also like to see far more use of nuclear power for electricity generation. That is something for another day perhaps.
We need more CO2, the plants and animals love it.

R Shearer
Reply to  Rod Evans
May 19, 2019 9:18 am

It’s a matter of thermodynamics and kinetics. The rate of drawing down is on average slower than the rate of emission. Overall life has the ability to proliferate and increase the rate of draw down to counter our fossil fuel emissions.

MS25
May 18, 2019 11:57 pm

Slightly off-topic,

Coccolithophores — tiny calcifying plants that are part of the foundation of the marine food web — have been increasing in relative abundance in the North Atlantic over the last 45 years, as carbon input into ocean waters has increased. Their relative abundance has increased 10 times,

This finding was diametrically opposed to what scientists had expected since coccolithophores make their plates out of calcium carbonate, which is becoming more difficult as the ocean becomes more acidic and pH is reduced.

So despite a tiny decrease in pH, the overall production of calcium carbonate increased 10-fold thanks to the additional CO2 plant food, which makes life for these little creatures so much easier. And same same story for plants at land.

https://www.sciencedaily.com/releases/2016/01/160116215419.htm

May 19, 2019 12:44 am

True!

I have a list of papers and articles about calcifying coccolithophores (and their happiness w/ higher CO2 levels), here:
https://www.sealevel.info/feedbacks.html#coccolithophore

commieBob
May 19, 2019 2:06 am

There is so much we don’t know.

Coccolithophores are one of the more abundant primary producers in the ocean. As such, they are a large contributor to the primary productivity of the tropical and subtropical oceans, however, exactly how much has yet to have been recorded. link

In spite of our important ignorance of basic facts regarding CAGW, we have scientists who insist that the theory is as solid as the law of gravity. Disgusting.

Ron
May 20, 2019 12:55 pm

“Coccolithophores are one of the more abundant primary producers in the ocean.”

Glad someone brought up the 800 pound gorilla in the CO2 “living room”..

80% of all photosynthesis, consuming CO2 and converting it to organic carbon, and carbonates (via their shells) takes place in the oceans. When they did the weight of their shells drag their organic mass to the bottom of the ocean.

I’m still a huge believer in the “Iron Hypothesis” put forth by the late Dr. John Martin. Trace Iron is deficient in so many parts of the ocean and it’s critical for phytoplankton to proliferate (feeding the marine food chain as a byproduct)..

May 20, 2019 1:46 pm

Ron, have you heard of a guy named Russ George?

http://russgeorge.net/

Russ George rejuvenated the Pacific salmon fisheries by fertilizing the ocean with iron sulfate. His experiment made a lot of people furious, mostly the sort of folks who are terrified by the idea of anyone doing anything at all without government or at least IRB review and approval. Here’s an article about his experiment, by a guy who hated the idea, but grudgingly admitted its success:

https://planetsave.com/2014/07/02/ocean-fertilization-dangerous-experiment-gone-right/

Ron
Reply to  Dave Burton
May 20, 2019 2:58 pm

Yep.. former CEO of Planktos, and the experiment in question that you refer to was done in conjunction with the Haida Indian tribe.. I believe they spent \$2 million to spread around 120 tonnes of Iron/Iron Sulphate and the Salmon harvest quadrupled the next year (2013)..

But the authorities referred to it as “ocean dumping” and raided his offices. Such BS..

One bit of curiosity though, with all the recent volcanic activity, and deposition of Iron laden ash, I’m wondering how that is impacting Phytoplankton blooms?

John Martin, IMO, deserves a Nobel Prize for his research on Iron fertilization. It’s a win/win scenario, completely controllable (stop fertilizing) and extremely beneficial to restoring the marine food chain that we’re over-depleting..

But no.. they want to spray calcium carbonate into the atmosphere to block the Sun.. but spreadimg Iron into the oceans in HN/LC zones is “dumping”..

I’d laugh if it wasn’t so disturbing..

https://earthobservatory.nasa.gov/features/Martin

Dennisa
May 19, 2019 2:17 am

as the ocean becomes more acidic and pH is reduced.

Which ocean?

May 19, 2019 4:26 am

Good point, Dennisa. Seawater pH varies much more from one ocean basin to another, and with depth, and over short periods of time, than the tiny 0.1 reduction in pH attributable to uptake of anthropogenic CO2:

Editor
Reply to  Dave Burton
May 19, 2019 5:22 am

That’s why Dissolved Inorganic Carbon (DIC or ΣCO2) and Total Alkalinity (TA) are the most commonly used metrics. Unlike pH, DIC and TA are unaffected by pressure and temperature.

In marine geochemistry, pH isn’t really that relevant. What matters is the calcite/aragonite saturation state. While pH can be calculated from DIC and TA, it varies widely with pressure, temperature and salinity.

Jim Ross
May 19, 2019 5:44 am

You also need to ask where in that ocean and when!

Annual variations in the surface ocean pCO2 can be much much larger than what we see in the atmosphere. Here is one example (wait for plot to appear):
https://pmel.noaa.gov/co2/story/GAKOA

Note the variation in pH as well, though sadly with limited data coverage.

Latitude
May 19, 2019 6:38 am

Coccolithophores —— have been increasing

Because they don’t have to work as hard….if these idiots would stop and study how it works…they wouldn’t look like constant idiots repeating themselves

Latitude
May 19, 2019 6:43 am

Coccolithophores……the sediments that formed the white cliffs of Dover….when CO2 levels were sky high

….and were so prolific…they formed those massive deposits

and……there was no ocean acidification to even dissolve the deposits

StephenP
May 19, 2019 1:16 am

What is/are the original source(s) of CA ions that react with CO3 ions to produce calcite?

On the outer Barcoo
May 19, 2019 12:08 pm

+What is/are the original source(s) of CA ions that react with CO3 ions to produce calcite?” Felspar minerals from basalt that decay via weathering into clay minerals.

Mark Pawelek
May 19, 2019 1:20 am

Please do not write these articles without including hydration and dissociation constants, and discussing what they mean.

Consider equation 1 first.

From wikipedia:

The hydration equilibrium constant at 25 °C is called K(h), which in the case of carbonic acid is [H₂CO₃]/[CO₂] ≈ 1.7 × 10⁻³ in pure water[5] and ≈ 1.2×10⁻³ in seawater.[6] Hence, the majority of the carbon dioxide is not converted into carbonic acid, remaining as CO₂ molecules.

[H₂CO₃] ÷ [CO₂] ≈ 1.2 × 10⁻³ (sea water) ≈ 0.0012.

Inverting it: [CO₂] ÷ [H₂CO₃] = 833. The ratio: CO₂ : H₂CO₃ = 833.

When carbon dioxide dissolves in sea water, at 25C, only 1 molecule in every 833 is hydrated to ‘carbonic acid’. At lower temperatures more CO₂ will be hydrated.

Consider equation 2 :

‘carbonic acid’ is a weak acid, which means most of it does not ionize to make acid.

2. H₂CO₃ (aq) « H⁺ (aq) + HCO₃&#8315 (aq). K(a1) = 2 × 10⁻⁴

Or: 2 × 10⁻⁴ = 0.0002 = [H⁺][HCO₃&#8315] / H₂CO₃. Inverting again. 1 ÷ 0.0002 = 5000 = H₂CO₃ / [H⁺][HCO₃&#8315].

For the small amount of ‘carbonic acid’ made in equation (1), only 1 molecule out of 5000 will create the acidic entity: H⁺.

The contribution from equation 3 is insignificant.

In Summary.

Taking equations 1 and 2 together. At 25C, for every 4,165,000 (4 million ~ 5000 × 833 ) molecules of CO₂ dissolving in sea water, only 1 extra acid ion H⁺ is made.

Only 1 extra acid entity for every 4 million CO₂ molecules dissolving in sea water. That’s why we can drink fizzy water without keeling over.

Mark Pawelek
Reply to  Mark Pawelek
May 19, 2019 2:07 am

&#8315 should be a hyphen-subscript ⁻

MFKBoulder
Reply to  Mark Pawelek
May 19, 2019 2:33 am

Good point,

This missing part in the article was my first thought as well. Wondering why a chemist would step in this trap.

commieBob
Reply to  Mark Pawelek
May 19, 2019 2:38 am

Good point. If you drive CO2 into fairly pure water under pressure, the most you can do is to make it slightly acidic. link

The Other Casper
May 19, 2019 11:28 am

Maaany years ago there was an experiment assigned to schoolchildren, where they would blow through a straw into a bottle of limewater (calcium hydroxide) and see a precipitate of calcium carbonate forming at the bottom. After much bubbling and giggling, the teacher would state something to the effect that this is how shellfish produce their shells.

The water remained alkaline throughout, and the children never exhausted the supply of calcium, because they got bored long before that point.

Reply to  The Other Casper
May 19, 2019 5:48 pm

“The water remained alkaline throughout”
Indeed. But the calcium carbonate precipitated. There is another stage of the experiment where you keep blowing and the water clears. That is the acidification phase. The CaCO₃ dissolves. pH still above 7.

The Other Casper
Reply to  Nick Stokes
May 19, 2019 8:29 pm

Once the solids have settled to the bottom of the ocean, however, the children have to assemble their straws together into a single very long one, and take turns on it, to get the second reaction to proceed.

It is also necessary to blow a little harder.

Reply to  Mark Pawelek
May 19, 2019 7:09 am

“only 1 extra acid ion H⁺ is made”
Totally irrelevant. The fraction of H⁺ in the sea is very small, whether made by CO₂ or not. The point is that CO₂ can react almost totally with the stronger base CO₃⁻⁻, converting it to HCO₃⁻. And it doesn’t matter whether it goes through an intermediate hydration. The conversion changes the solution equilibrium of CaCO₃.

Robert W. Turner
Reply to  Nick Stokes
May 19, 2019 12:06 pm

Completely relevant. A strong acid with more complete dissociation would change the equilibrium by quite a bit more.

Reply to  Robert W. Turner
May 19, 2019 4:40 pm

Not true. CO₂ converts one molecule of CO₃⁻⁻ to HCO₃⁻. HCl converts one molecule of CO₃⁻⁻ to HCO₃⁻. It can do no more.

That’s the point of a buffer. No acid, however strong, can be more effective than the buffers acid species. because it immediately reacts with the buffer base, and is thus replaced by the buffer acid.

R Shearer
Reply to  Nick Stokes
May 19, 2019 5:08 pm

CO₂ + CO₃⁻⁻ = CO₃⁻⁻ + CO₂

Mark Pawelek
Reply to  Nick Stokes
May 19, 2019 10:22 pm

a. Yes. With pH = 8, alkaline [OH⁻] is 100 times acidic [H⁺]. Sea water is alkaline, never acid. It’s a mystery how any self-respecting scientist can talk of ‘ocean acidification‘, as if it’s a thing.

b. The concentration of, stronger base CO₃⁻⁻ is limited by its low solubility. In pre-industrial sea water [HCO₃⁻] is about ten times [CO₃⁻⁻]. If [CO3⁻⁻] declines, more will dissolve from vast reserves of dead carboniferous creature shells sitting on the bottom of the seas.

The Other Casper
Reply to  Mark Pawelek
May 19, 2019 8:23 am

But the equilibrium of Equation 1 is being “driven to the right” by the reaction in Equation 5 (once 2 and 3 have occurred). These act to remove the product of 1, H2CO3.

The product of 5 is a solid, CaCO3, which for practical purposes falls out of the picture, because it has no “concentration” in solution. The whole set of reactions continues rightward until an appreciable fraction of the dissolved Ca++ has been replaced with H+ in solution, and then we’d see some “leftward pressure” extending back to 1.

The Other Casper
Reply to  The Other Casper
May 19, 2019 9:23 am

Sorry, by “the whole set of reactions continues rightward” I meant Equations 1, 2, 3, and 5.

Robert W. Turner
Reply to  Mark Pawelek
May 19, 2019 11:54 am

Thanks you!

And a nitpick, equation 5 should be
5 – Ca++ + CO3– – CaCO3 (calcium carbonate) – not (calcite)

The actual mineral form is never pure CaCO3, it ranges from low magnesium calcite (not relatively abundant today), high magnesium calcite, aragonite, vaterite, ikaite, and dolomite. In today’s oceans with relatively inactive hydrothermal circulation within the ocean crust, most of the species occurs as high magnesium calcite to aragonite.

Alasdair
May 19, 2019 1:33 am

Thanks for that Daniele. Much appreciated. Have the gist but light on comprehension.

This paper should be required reading for all those budding, scuba diving , wannabe Phd students, hell bent on stuffing their computers with observations designed to reinforce their emotional conclusions.

TFN Johnson
May 19, 2019 1:57 am

The last two comments are part of my question, which was to be “what about all the zoic Ca, precipitated as bones and shells?”.
It would helpful if geologists use limestone to refer to azoic CaCO3, and chalk for all the zoic CaCO3.

Mark Pawelek
May 19, 2019 2:06 am

Please do not write these articles without including hydration and dissociation constants, and discussing what they mean.

Consider equation 1 first.

From wikipedia:

The hydration equilibrium constant at 25 °C is called K(h), which in the case of carbonic acid is [H₂CO₃]/[CO₂] ≈ 1.7 × 10⁻³ in pure water[5] and ≈ 1.2×10⁻³ in seawater.[6] Hence, the majority of the carbon dioxide is not converted into carbonic acid, remaining as CO₂ molecules.

[H₂CO₃] ÷ [CO₂] ≈ 1.2 × 10⁻³ (sea water) ≈ 0.0012.

Inverting it: [CO₂] ÷ [H₂CO₃] = 833. The ratio: CO₂ : H₂CO₃ = 833.

When carbon dioxide dissolves in sea water, at 25C, only 1 molecule in every 833 is hydrated to ‘carbonic acid’. At lower temperatures more CO₂ will be hydrated.

Consider equation 2 :

‘carbonic acid’ is a weak acid, which means most of it does not ionize to make acid.

2. H₂CO₃ (aq) « H⁺ (aq) + HCO₃⁻ (aq). K(a1) = 2 × 10⁻⁴

Or: 2 × 10⁻⁴ = 0.0002 = [H⁺][HCO₃⁻] / H₂CO₃. Inverting again. 1 ÷ 0.0002 = 5000 = H₂CO₃ / [H⁺][HCO₃⁻].

For the small amount of ‘carbonic acid’ made in equation (1), only 1 molecule out of 5000 will create the acidic entity: H⁺.

The contribution from equation 3 is insignificant.

In Summary.

Taking equations 1 and 2 together. At 25C, for every 4,165,000 (4 million ~ 5000 × 833 ) molecules of CO₂ dissolving in sea water, only 1 extra acid ion H⁺ is made.

Only 1 extra acid entity for every 4 million CO₂ molecules dissolving in sea water. That’s why we can drink fizzy water without keeling over.

Barry Hoffman
May 19, 2019 4:23 am

Mauna Loa Observatory is the Gold Standard for atmospheric CO2 measurement (415 ppm). The observatory is at 3400 meters altitude. It is surrounded by a relatively warm ocean. What is the CO2 measurement over Antarctica at 3400 meters altitude? Or do we assume 100% atmospheric mixing and just move along…..

Jim Ross
Reply to  Barry Hoffman
May 19, 2019 5:35 am

The South Pole observatory is at 2837m amsl and the current CO2 reading is 406 ppm. It tracks the increase at Mauna Loa very closely, though with a very small difference in growth rate.

http://scrippsco2.ucsd.edu/graphics_gallery/mauna_loa_and_south_pole/mauna_loa_and_south_pole

Kaiser Derden
May 19, 2019 4:55 am

the idea that CO2 is a well mixed gas has always been a childish assumption that the satellites have now shown to be nonsense … the idea that CO2 is evenly dissolved in the oceans is another childish assumption that doesn’t even begin to hold up under the most basic observation and measurement … just like a “global temperature” … its just one flawed assumption built on another and another and another … its turtles all the way down in the world of climate “science” …

Editor
Reply to  Kaiser Derden
May 19, 2019 5:25 am

It’s relatively well-mixed in the atmosphere, above surface effects. Now the pCO2 in the oceans can vary widely, although, on average, the surface waters partial pressure is equivalent to the atmospheric concentration.

Clyde Spencer
Reply to  David Middleton
May 19, 2019 10:56 am

David
“relatively well-mixed” is qualitative and ‘in the mind of the beholder. I think that we should try to stick to quantitative representations, i.e. some mean value +/- 2SD. The key to defining the term “relatively well-mixed” is the standard deviation.

Anthony Banton
Reply to  Kaiser Derden
May 19, 2019 6:49 am

“the idea that CO2 is a well mixed gas has always been a childish assumption that the satellites have now shown to be nonsense ”

Couldn’t be further from the truth …..

“Fig. 1
Time series and global maps of satellite observations of atmospheric carbon dioxide (colour figure online)”

Michael Jankowski
Reply to  Anthony Banton
May 19, 2019 7:26 am

…”Contrary to prevailing wisdom, CO2 is not well mixed in the mid-troposphere,” said Moustafa Chahine of the NASA Jet Propulsion Laboratory (JPL), AIRS’s principal scientist…

Mark - Helsinki
Reply to  Anthony Banton
May 19, 2019 7:27 am

I’ve measured CO2 many times at many locations, and readings can be different from place to place.

At higher altitudes it is better mixed, at ground level, you can get very different readings depending on where you are.

Well mixed.. depends on altitude in my experience

Mark - Helsinki
Reply to  Anthony Banton
May 19, 2019 7:30 am

the mixing can depend on several factors and one of the most important is the concentration of CO2.

If CO2 is sufficient in concentration (without being pressurized in any way), it will push the air away, not mix well with it.

Clyde Spencer
Reply to  Mark - Helsinki
May 19, 2019 11:03 am

Mark – Helsinki
That is, it stays near the ground and pools in low spots. It is a known hazard in volcanic source areas. There has to be wind to disperse it.

Michael Jankowski
Reply to  Anthony Banton
May 19, 2019 9:35 am

Even better…here’s the actual GOSAT time-lapse data that was part of the figure you linked to. Hard to argue “well-mixed,” especially when you look at portions of Africa and South America.

http://www.gosat.nies.go.jp/en/global_ghg_simulation.html#globalco2simulation

Things look better using a gridded image because…well, as the time-lapse video shows, relatively high levels of CO2 and relatively low levels of CO2 are often in the same grid cell.

In other words, the gridding process used to derive the figure you reference is doing much of the “mixing.” The reality is much different.

Anthony Banton
Reply to  Michael Jankowski
May 19, 2019 12:08 pm

“Hard to argue “well-mixed,” especially when you look at portions of Africa and South America.”

On the contrary.
The CC is a flow of CO2 twixt sources and sinks and looking at that on a seasonal basis, driven by surface temperature and biosphere changes, that vid shows the influence of the NH landmasses in summer reduction in CO2 (O2 production) and the flip in winter of CO2 production. The SH being predominantly ocean does not exhibit that effect to anything like that degree.
In short looking at the mixing of CO2 in the biosphere must exhibit differential concentrations on a seasonal basis, but ends up mixed after the completion of each yearly cycle.
Well mixed … such that the carbon cycle of the planet can allow.
And also note the anthro CO2 production over industrial areas (vis China).

Well- mixed, such that even the the seasonal cycle in the NH is visible down at the north pole …..

Michael Jankowski
Reply to  Anthony Banton
May 19, 2019 3:01 pm

Not sure what planet you are on…when you have large locations with high values and low values consistently separated by a few hundred miles as the video displays, you’re not “well-mixed.”

Yes, the video shows “anthro CO2 production over industrial areas (vis China).” And guess what? There is often a huge low spot of CO2 right adjacent to it…often among the lowest (bluest) values at that time in sharp contrast.

The video contradicts you, as does the NASA finding.

Smart Rock
Reply to  Michael Jankowski
May 20, 2019 7:16 pm

This one-year record shows higher resolution in both time and space, plus it shows the whole globe all the year:

Even allowing for the distortion due to using Mercator projection, it looks as if the boreal forests of Siberia and Canada do more CO2 reduction than the tropical rain forests. Possibly because they are in relatively cold climates and there’s less rotting of dead vegetation.

A lot of what look like point sources of CO2 in the Congo basin (slash-and-burn agriculture?), much more than in the Amazon basin.

tty
Reply to  Anthony Banton
May 19, 2019 2:56 pm

Depends on what you consider “well-mixed”. Here is a readable map by the way:

May 19, 2019 5:11 pm

Note that the range is from 387 to 403.5 ppm. That is well mixed.

Clyde Spencer
Reply to  Nick Stokes
May 19, 2019 8:54 pm

Stokes

Without an accepted definition of “well mixed’ we can argue forever about whether or not CO2 is well mixed. How does it compare to nitrogen or oxygen? If it varies more than N2 and O2, than an argument can be made that at least is it not as ‘well mixed’ as the two primary gases.

Where is the anomalous CO2 off the SE coast of Greenland coming from?

Reply to  Nick Stokes
May 19, 2019 9:45 pm

“Well mixed” here means that you can reasonably use the average value for computing the greenhouse effect globally. And with a range of variation well under 5%, that seems very reasonable.

The SE Greenland blip is right on the border of what they consider the satellite can see reliably. It may not be real. Or it could be a wandering of the Gulf stream, mixing with the Labrador current with outgassing. But I’m doubtful.

Bob boder
Reply to  Nick Stokes
May 21, 2019 11:38 am

Clyde

sorry that’s well mixed by pretty much everyone’s definition.

Reply to  Nick Stokes
May 21, 2019 11:52 am

Yes, I would say CO2 is “pretty well mixed,” except in the immediate vicinity of strong sources or sinks.

Tom Halla
May 19, 2019 6:52 am

The post seems to only consider inorganic processes for CO2. Various calcareous algae and assorted shelly fauna actively absorb CO2, and sequester it to some degree.

Mark - Helsinki
May 19, 2019 7:24 am

Ocean acidification is junk science.
1. To acidify sea water with CO2 directly, it takes a LOT per liter, and the supply must be constant.
2. The instability of carbonic acid in aqueous liquids means very little acidic ions are released
3. For temperatures to concentrate the acidic ions sufficiently to be an issue (not considering buffering) requires temperature to approach the mid 20s centigrade.
4. There is not enough CO2 in all of the coal and oil left to acidify the oceans
5. Sulfur has a much bigger impact on the oceans than CO2 ever will.
6. Current buffering capacity of the oceans, earth’s crust, ocean life and huge venting events like with El Nino that can cause geometric CO2 growth to spike at Mauna Loa, makes it impossible for this to be a problem
7. No evidence from history that atmospheric CO2 has been a problem for the oceans
8. We have nowhere near enough data to even approach this topic in any meaningful way.
9. Slow warming of the oceans as is currently happening, causes a net loss of CO2, atmospheric levels not increasing even remotely fast enough to counteract the release of CO2. again see El Nino 2015/16

I’ve been managing CO2 driven pH and water in reefs and fresh water for over 20 years in small closed systems where things happen much faster.

OA is plan B, if the warming stopped, then OA would be the bogey man and the money faucet and scaring can continue unabated.
It’s junk science from top to bottom.

Ron
Reply to  Mark - Helsinki
May 20, 2019 3:17 pm

And not only junk science, it’s manipulated.. PH varies in any portion of ocean water throughout the day.. If you want a certain reading that meets your preconceived conclusions, just wait for the “optimal” time period.

In addition, PH varies according to the region of the various oceans on a fairly significant scale (but still around PH of 8)..

It was discussed here in 2012.. Coastal PH levels are have diurnal changes throughout the day, depending on phytoplankton populations and upwellings.

And as an aside, one of my pet hypothesis’ is that Coral Bleaching is just as much the result of inadequate Iron in the tropical waters to promote growth of their Algae “symbiots” (zooxanthellae) upon which the polyps derive the majority of their energy. Would love to test that hypothesis one day (spending endless hours diving on remote beautiful coral reefs.. ;0) )

Are the Corals actually in a state of Chlorosis (iron deficiency), like much of the rest of the oceans, is what I wonder.

https://wattsupwiththat.com/2012/01/09/scripps-paper-ocean-acidification-fears-overhyped/

https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3813339/

Robert of Texas
May 19, 2019 7:45 am

Yeah! Another juicy posting ripe for me learning something new! 🙂

“Actual atmosphere contains around 850 Gt (giga tonn) of carbon (in form of CO2) while the oceans 38000 Gt of carbon, nearly 45 times more.”

I am always bothered by statements like the above as I know these are just educated guesses and I do not understand just how much real knowledge goes into producing them. For example, does the atmosphere contain about 850+/-50 Gt CO2, or is it more like 850+/-300 Gt? Or is this a low ball range, or a high ball, or a guess at an average? The ocean guess is likely even more of a guess (I am guessing!). Near underwater hydrothermal vents the CO2 concentrations are much higher, and I suspect there are far more of those than anyone accounts for.

What about methane clathrates? That carbon has to come from somewhere, I assume its coming from the ocean waters…but isn’t that a storage reservoir of carbon no one is considering? Kind of like calcite, it could be considered a long term storage reservoir of carbon that cannot be directly measured in sea water. (for example, there could be miles of limestone deposits forming in the silts at the bottom of the oceans)

Another huge reservoir I rarely hear mentioned (because no one really understands it) is the water contained in the actual crust rock which could have even higher amounts of dissolved CO2 in it (at pressure).

So while we can make an educated guess at how much carbon is in the oceans, I don’t see how we can make a guess at how fast it is being placed into a long term storage medium.

OK, on with studying this post…just wanted to get that out of the way.

Mark - Helsinki
Reply to  Robert of Texas
May 21, 2019 12:46 am

factor in carbon sinks in the oceans, and boom, it’s FAR more than 45 times

Robert of Texas
May 19, 2019 8:15 am

“Next figure 2 indicates how temperature affects the inorganic carbon equilibria at constant CO2 (400 ppm). With increasing temperature the DIC or C(T) (total dissolved inorganic carbon) decreases and pH increases.”

This chart assumes CO2 is at equilibrium, so they only variable changing is temperature. The conclusion that as temperature rises the pH also rises makes sense; but the oceans are not at equilibrium with the atmosphere (demonstrated later) so you COULD get a lowering of pH even though temperature is rising as the ocean continues to absorb CO2 until reaching an new equilibrium.

The problem with all of this chemistry is the time scale. Natural processes often move at geologic time, while humans can’t even conceive of these time scales. So while the processes to reach equilibrium and store excess carbon move forward, we may not notice in our short lifetimes.

Humans are adding some estimated 4% of the total CO2 emitted into the atmosphere (another one of those annoying mysterious guesses). What I would like to know, is how 4% can make any noticeable difference to a natural system that likely deals with periods that are +/-25% of what we call normal. Large volcanic eruptions, rifting, and who knows what else… CO2 is undeniably rising in the atmosphere – something is causing it – human activity is really convenient to blame – but I remain unsure that there is not a natural process causing most of it, such as degassing from the oceans.

The fact that an “average” calculation shows the ocean can hold more CO2 does not mean there is not a natural process ongoing that is releasing CO2 from the oceans. For example, let’s say on average the ocean temperatures and CO2 concentrations mean (on average) it can absorb more CO2, but there is an ocean conveyor that is pushing cold more saturated waters up and they are warming so much they release CO2. This could permanently keep the levels of CO2 low (on average) – equilibrium of the average be damned. If this process were to shut down (the conveyor stop or just move) then the ocean could suddenly absorb more CO2 without releasing as much until equilibrium.

It’s these natural processes all working together that make any simple calculation almost pointless. We have to understand the whole – not just the chemistry of CO2.

I guess we could always build a model! 🙂

Ossqss
May 19, 2019 9:57 am

It is just a matter of time until the Climonista come after other carbon footprints. So, how about we get ahead of the curve and determine the impact of beer production on ocean chemistry in preparation. What is the CO2 footprint of beer anyhow? We sure do make a bunch that makes CO2 during the fermentation process……

https://www.statista.com/statistics/270275/worldwide-beer-production/

There would be many more colors of vests protesting an assault against beer than just yellow ones I believe! 😉

Peter Foster
May 19, 2019 1:40 pm

Limestone formation takes about 9 Gt/year of CO2 out of the marine ecosystem in the form of microscopic shells formed by organisms like foraminifera. This does not seem to have been included in the calculations and this removal of carbonate probably far exceeds that from chemical precipitation. The increase in limestone is about 40mm/1000 years over all the oceans but not below depths of 4500m (see below)
Secondly taking a average sea temperature does not help much, When he thermohaline circulation surfaces it is bringing deep ocean waters from below 4500 m that are super saturated with carbonate. (precipitates of CaCO3 and shells of marine organisms redissolve below the carbonate compensation depth of 4500 m) When this water warms near the surface the release of dissolved CO2 will be substantially greater due to a number of reactions, among them the reaction of
CO2 + CO3 + H20 = 2HCO3 (sorry cant do superscript charge signs).
The increase in HCO3 will then drive the
CO2(aq) + 2H20 = HCO3 + H3O
to the left and solubility change with increased temperature will release the extra CO2 to the atmosphere.
The bottom water is at 4°C so increasing that to 17 °C would release a lot of CO2.

What proportion of water is in this situation I have no idea but the amount of cold water coming to the surface must in the end equal the amount of surface water that descends to the depths during the annual formation of sea ice, particularly around Antarctica.

tty
May 19, 2019 3:00 pm

What are those big industrial areas in the Congo and Amazon basin?

Marcus
May 19, 2019 5:15 pm

Elephant farts ?

Clyde Spencer
May 19, 2019 8:58 pm

tty
And off the SE coast of Greenland?

Steve O
May 19, 2019 4:37 pm

If the equilibrium level is so low, why are there such long, extended periods when the CO2 levels were much higher than they are today?

May 19, 2019 6:15 pm

Manau Lo is not a good location from which to measure CO2, so how was
it selected. Its Tropical and has Volcanos close by.

Why not use the mountains of Tasmania, a large Island South of the
Australian mainland. It has many thousands of miles of Ocean to its West,
and its cool.

Also its about time that we downgraded the role of Metorogolests in telling
us about climate, plus their words of wisdom about CC.

Its the experts on matters within the vast Oceans, all 73 % who have the
key to what affects the weather of this planet.. Oceans and their ability to
store vast amounts of heat energy from the Sun which drives the wether, its
not the atmosphere.

MJE VK5ELL

Dave
May 20, 2019 8:49 am

May I suggest the author of this post read through Geochemistry of Sedimentary Carbonates by Morse and Mackenzie or one of the carbonate review articles by Morse.

JERRY HENSON
May 20, 2019 11:19 am

Several fallacies exist in the attempt to understand the carbon cycle.

One is that upland soils absorb methane from the atmosphere.

This is listed in past USEPA carbon budget as a 30 Gt annual sink.
It is not. The hydrocarbons found in the upland topsoil rise from
deep in the earth and are the main way that subducted carbonates
are recycled. The hydrocarbons are mostly oxidized in the topsoil,
in the presence of adequate moisture and rise as CO2.

I have previously described the simple test I use to prove this
fact. Another simple test I recommend to disbelievers as a step
to enlightenment is to clear a patch of rich upland soil of
grass, etc. and invert a 12 inch stainless steel bowl to which
you must glue an additional 6″ plastic skirt, put your CO2 meter
under it on continuous read, weight down the skirt with sand,
to prevent any wind from sucking the CO2 out, and weigh the
bowl down with a 10 lb. weight. Twelve hours later, retrieve the
meter.

On my property in east Tennessee, one such experiment started
with an ambient reading of 403 ppm CO2, and at the end of 12 hrs.,
the reading was 960 ppm CO2.

This will not work well if your soil is red clay. If you live in an area
that is arid or semi-arid, and the shield is not near the surface, do
the same test with a hydrocarbon test meter.

The hydrocarbons rise in desert areas where the shield is deep
enough, but moisture is required for the microbial culture to
thrive, to convert the hydrocarbons to CO2.

The people who find CO2 readings in their research and think
that it came from plants are wrong. Once plants absorb CO2,
they do not exhale or emit it until they die, and microbes
convert their mass first to methane and then to CO2.

A couple of the researchers who misunderstood CO2 and
methane readings in their tests are cited below.

They included soil in the gas capture.

The oceans will not become acidic. As the CO2 load in the oceans go up,
CO2 concentrates at depth, and you get, as someone mentioned above,
the cliffs of Dover.

Besides that, Le Chatelier has a rule against that.

Bob Weber
May 21, 2019 6:27 am

This was a very interesting article and I enjoyed reading all the various POVs. Chemistry was a favorite subject 40 years ago.

This morning I withdrew my abstract from the upcoming AGU Chapman Conference on Understanding Carbon Climate Feedbacks because of one mistake I made hastily right at the deadline- a personal disappointment and lesson learned. I’m not happy about it because I had worked out the things I referred to in my comments above in direct response to a personal challenge by Gavin Schmidt made at the 2018 LASP Sun-Climate Symposium. So believe me I was very motivated. The good takeaway is there will probably be another such conference next year, so the works presented from this year’s event can be studied for another year, and I can refine my work that much more.

You’d think since the ‘science is settled’ there’d be no need to have any more conferences! Based on all the divergent views expressed here on the subject this science is not settled by any means.

As I previously said yesterday, NASA’s numbers only add up if we believe Henry’s Law can be violated for decades, essentially nullifying it as a physical law, something I don’t abide in. There’s something very definitely wrong with their carbon budget picture as presented.

Hunter Paalman
May 21, 2019 9:33 am

Thank you many gentlemen and several ladies for this truly entertaining ramble through some “Aquatic Chemistry” features that decorated my professional life for many decades. I cut my teeth on sea water purification, then graduated to oil field connate waters processing for iodine recovery and later dealt with environmental remediation of the spent stream for discharge or its sterilization as reinjection water to mitigate bacterial contamination and sulfide corrosion during secondary production.

When energy resources were in doubt, I was tasked in support of geothermal energy development. I got into hot waters east of the Sierra and got more familiar with a hotter resource set in Nevada’s Basin and Range region. Finally, this track led to the hyper saline brines of the Imperial Valley and Mexico. Many technical chemical and engineering challenges were encountered and some successes too. Latter years dealt with environmental remediation and even a glimpse into the Casmalia Super Fund Site horror story in search of a redemptive happy ending.

That was lots of good chemistry and bad in a career full of challenges and fun. Again “thanks for the memory.”