Algorithms in Ocean Chemistry: a review

By Rud Istvan,

Italian physical chemist Daniele Mazza recently sent WUWT a draft of his new ebook on seawater chemistry, seeking WUWT input. Charles asked me to review, since he knew I had previously published on ‘ocean acidification’. I have now done so, and my thinking follows. For those wanting a deep dive on ocean physical chemistry, this new ebook is a much better and more detailed explanation than I could ever hope to provide (started college intending to be a chemistry major, rapidly switched to economics with an emphasis on all forms of mathematical models, not just in economics). But it perhaps lacks nuanced secondary and tertiary ‘Jim Steele’ ocean biological perspectives. For those wanting an oversimplified laymen’s overview of those, see my essay ‘Shell Games’ in ebook Blowing Smoke, especially the paragraphs concerning Florida Bay seasonal ocean chemistry concerning ocean chemistry parts 1 and 2.

Ocean Chemistry (1)

Ocean acidification is a deliberate misnomer, since the oceans are basic and will always remain so thanks to igneous rock chemical weathering and rivers. A slight reduction in basic pH never gets close to true acid (pH<7)– although there are special small locality exceptions thanks to volcanism. The Bubble Bath off Dobu Island is the example in essay Shell Games.

Ocean pH chemistry is very complex, because the oceans are highly buffered. This obvious fact was ignored in IPCC AR4, which reached a grossly wrong (by factor >2x) ‘acidification’ conclusion. Mazza’s new ebook does a very good job of simply explaining the ocean’s buffered chemistry complexities, and thus AR4’s unforgivable basic ocean chemistry science mistakes.

Another basic physical chemistry consideration is oversaturation of seawater in respect to both the aragonite and calcite forms of CaCO3. The precipitation of these crystalline solids is the final chemical/biological outcome of seawater-dissolved CO2.

Ignored by Great Barrier Reef Catastrophists.

Ocean Chemistry (2)

But in the photic zone (roughly the first 100-150 meters where light can penetrate to enable photosynthesis), ocean chemistry and pH is much more driven by biology than by basic physical chemistry.  Photosynthesis consumes dissolved CO2 and produces hydrocarbons, carbohydrates, and calcium carbonates like coccolithophore exoskeletons. The entire ocean food chain depends on photic zone photosynthesis, which naturally slightly raises ocean surface water pH.

And for a few hundred meters below the photic zone, biological decomposition of this ‘rain’ of photosynthetic plant matter naturally slightly lowers pH while recycling nutrient ‘fertilizer’. Which is why upwellings of this colder, nutrient rich, lower pH water produce visible phytoplankton blooms on the surface until the nutrients and dissolved CO2 are again consumed by phytoplankton, which raises the photic zone pH. For example (illustrated in my essay), along the US West Coast thanks to wind driven Eckman transport currents. Like at Netarts Bay, Oregon (see below).

Ignored by Great Barrier Reef catastrophists.

Ocean Chemistry (3)

At least all shallow water (estuarine) marine organisms have evolved with this ‘pH knowledge’. The Miyagi oyster did; the Netarts Bay Whiskey Creek oyster hatchery problem arose because it is not an estuary, and was improperly not managed to mimic one. Its much ballyhooed ‘ocean acidification’ problem was warming the naturally lower pH upwelling ocean water to induce Miyagi spawn WITHOUT also increasing pH to what naturally incurs in summer estuaries where and when Miyagi oysters naturally spawn. Whiskey Creek hatchery has othing to do with CO2 emissions and ‘ocean acidification’. The gross error arguably comprises inexcusable academic misconduct (knew or should have known) from PMEL and U. Oregon.

Even more relevantly, Jim Steele has provided WUWT much biological evidence that coral polyps manage their internal calcification pH to minimize surface reef pH fluctuations. Else how could corals have survived for so many millions of years despite experiencing fluctuations in sea level and seawater pH?

This observation also explains why corals reproduce two different ways: asexually via budding, and once a year sexually via spawning. Buds carry the epigenetics of locally adapted polyp variations to repopulate a local bleached reef. Polyp spawn carry their underlying DNA to newly populate a distant reef sometime later, and then eventually develop there a new locally adapted epigenetics. Nature is amazing.

For a learning digression on epigenetics, see my 2017 essay concerning the agricultural development of Mesoamerican dry beans at Climate Etc: “ A beneficial climate change hypothesis”.

Ignored by Great Barrier Reef catastrophists.

Regards to all. My cryptic review comments are meant to facilitate your own research, not to retrace my own very meandering learning journey on this topic.

58 thoughts on “Algorithms in Ocean Chemistry: a review

  1. Well, emphasizing that the photic zone is dominated by biology rather than aqueous chemistry, is a darned good start.

  2. the oceans are highly buffered…..and that’s an understatement

    just try to get them to understand where the carbon comes from…that really messes them up

  3. “Jim Steele has provided WUWT much biological evidence that coral polyps manage their internal calcification pH to minimize surface reef pH fluctuations”

    The polyps have what all other life has, physiological power, that allows them to control their internal pH. It is the voluntary ignorance of the many alarmists to assume that life is completely and intimately at the mercy of their surroundings. Of course, there are ranges of tolerance and ability, but life that has been around this long in the oceans surely has the potential to deal with variations in seawater pH.

    Ocean pH is usually 8.2–8.4, but during a sunny day in an estuary or bay the pH can rise above 10, as photosynthesis is an alkalizing process. During the might, aerobic metabolism, which is an acidifying process, bring the pH back down.

    Also, coral reefs survive by having ocean waters flow through them, more or less constantly, from which they filter food. How often are we reminded that ocean water might enter a coral reef at pH 8.4 but, after passing through the reef, has pH 8.0 or less? We should be reminded often. The many living organisms in the reef emit a wide range of organic acids that lower the pH, yet everybody is happy and healthy. That’s life!

  4. this is the absolute largest system on Earth of Mother Nature’s biochem at her very best – great post – thank God – whoops I mean thank you to Mother Nature and then this amazing blog – for bringing truth into this area of BS factor – ocean acidification misnomer. A v. big cheers – the truth always prevails in Science – even if it takes centuries until they can’t possibly lie anymore – once the mob turn – that’ll it be it for all those making a dodgy living out of this absolute unsubstantiated and completely lacking in evidence null and void hypothesis – and really calling it a hypothesis is an insult to the scientific method process – since there’s zero evidence to support their dodgy predictions and the CO2 one is completely non-falsifiable –
    all due to the advent of computer modelling – otherwise this would never have happened again in the history of science – who would’ve thought in the 20th and now 21st century that application to the scientific method would go out the window completely – Not Lavoisier or any other of those great scientists whom worked so hard to ensure that application to the scientific method was the only way to go to keep science away from the charlatans – they’ll be turning over in their graves

  5. Too many “experts” are unable to come to terms with complex biological systems, being more comfortable in the “hard” sciences of chemistry and physics. The Earth system is regulated so well by the web of life. It maintains an atmosphere and oceans with stability for hundreds of millions of years, and is able to recover and thrive following catastrophic events due to life’s resilience.

    The classic joke is the physicist who begins to solve a biology problem with, “assume a spherical cow in a vacuum….” My experience is the joke is on the poor physicist who figures a biology problem will be merely annoying, because it couldn’t be particularly hard.

    It is refreshing to read a post that clearly was written by someone comfortable with biology and knowledgeable about chemistry.

  6. Um, can we get to the book through some method that does not require me to log into Google? (or Facebook which I refuse to use at all) I hate supporting Google in any way, but would really like to read this paper.

    I think we are all “Ocean Blind” because we are land animals, but it is the ocean that really runs climate. The atmosphere is just a heat-conductor to the main engine. I suspect the ocean plays a really big role in atmospheric CO2 concentrations as well, while man plays a tiny role. This will all eventually be discovered (or disproved) but not by the current generation of biased climate scientist idiots.

  7. It would be great if WUWT copies this post to Roger Harrabin. He has been banging on about about ocean acidification at least since 2008. Telling Roger that corals formed in the precambrian seas has had zero effect on him or his flawed logic. Sadly, his degree in English may not equip him sufficiently to appreciate this useful paper.

      • You are known for your bite and your comment was particularly sharp-toothed. Yes, sadly I cam to a similar conclusion some time ago. However, if you know the story of the camel, the water and the bricks maybe there could be another outcome.

  8. While not exactly about the topic in this excellent essay, the following relates to the subject matter. I would appreciate any reality related comments as to whether the referenced analysis makes sense or has some serious flaw(s).

    The basics of the generally accepted view on atmospheric CO2 concentration is that sampling measurements show atmospheric CO2 concentration increasing over time. Based on the sample measurements, estimates of total quantity of the atmosphere, and estimates of total human emissions of CO2, the consensus is that about 50% of human CO2 emissions end up in the atmosphere long term. Also the generally accepted view is that much of the other 50% ends up in the oceans. I know there are other hypothesis about atmospheric CO2 but I don’t care at the moment unless they explain something about my question.

    Two essays by Chaamjamal
    2018: https://tambonthongchai.com/2018/09/29/ocean-acidification-by-fossil-fuel-emissions/
    2019 update: https://tambonthongchai.com/2019/12/14/ocean-acidification-2019/

    Using 124,813 measurements of ocean CO2 concentration from 1958 to 2014 made by Scripps Institution of Oceanography

    based on
    • the measured annual ocean CO2 concentration changes from 1958 to 2014,
    • the measured CO2 concentration depth profile,
    • and the measured total CO2 ocean concentration changes from 1958 to 2014

    the essays concludes that the data does not support the hypothesis that the ocean CO2 changes are due to human emissions. It would, by the essay calculations, require about 22 times 100% of the total human emissions from 1958 to 2014 to achieve the measured ocean CO2 concentration changes, thus the increased ocean CO2 content must come primarily from some other source.

    Is there some data, calculation, or logic error in that conclusion or is this just something very inconvenient and thus ignored by current climate science?

    • Hi Andy: This 50/50 idea derives from a number of false assumptions made by IPCC. One relates to the assumption that (1) ALL the increase in atmospheric CO2 (the Keeling curve) results from anthropogenic emissions another that (2) the residence time of CO2 in the atmosphere is many times the measured values (i.e greater than 100 years compared with measured values in about 35 experiments that concluded a range of values up to 25 years with the best guesses around 5-6 years). It is totally wrong thinking as regards the fate of the anthropogenic emission component. In reality CO2 coming from human sources simply joins in with the very much greater natural emissions and the whole of the variable atmospheric CO2 is available for sequestration by a number if processes with different mechanisms in play and different time constants. It is true that biggest reservoir of CO2 is the worlds oceans but equally in a warming world it is also the biggest emitter. Actually I am currently preparing something on this subject, particularly Henry’s Law that should completely answer your points but this will not be ready for some time. IPCC also use a misleading argument about the ratio of C12 /C13 to support its failing hypotheses. The latter can easily be dismissed but that’s another story. Regards Peter

      • This 50/50 idea derives from a number of false assumptions made by IPCC.

        That is not correct, Peter. Anybody can calculate the airborne fraction (AF) by simply dividing the amount of CO2 emitted in ppm every year by the increase in atmospheric CO2 every year. My calculations give the same result as those by James Hansen, since we use the same sources (Boden & Marland for emissions, and Mauna Loa for atmospheric increase). AF has been decreasing over time:
        https://i.imgur.com/NkwBzfj.png
        Which indicates sinks have been increasing faster than our emissions.

        • Javier: There are many ways to be wrong and it is probably very difficult to be correct as science is never settled except in the works of IPCC. In this case you have missed the point. To get it you must first determine how much CO2 is emitted naturally and how much is emitted anthropogenically to a first approximation these should be added together at the start. BUT in the case of the water reservoirs these are not independent as Henry’s Law is concerned with the partial pressure of the gas over the liquid so at any one temperature water emissions can in principle be reduced by the increase in anthropogenic emissions. This is quite apart from the rather complicated water chemistry. As we have been in “lockdown” for some time and human emissions have decreased if IPCC were correct then a reduction in gradient of the Keeling Curve would be expected. I have been watching and unless there is to be a future “adjustment” then no such change in gradient has occurred. Some of us may have some further conclusions about the reasons. Friend Murry Salby is watching too. No doubt he will have some comments soon too. The above sidesteps the other issue I hinted at with respect to sequestration processes but I think I will leave this to another time and I am busy preparing something a bit wider. Regards Peter

          • To get it you must first determine how much CO2 is emitted naturally and how much is emitted anthropogenically to a first approximation these should be added together at the start.

            No you don’t. Considering only the atmosphere:
            Δ[CO₂]nat + Δ[CO₂]ant = Δ[CO₂]atm
            Since Δ[CO₂]ant = 2 x Δ[CO₂]atm, then –(Δ[CO₂]nat) = 1/2 (Δ[CO₂]ant)
            When don’t need to measure Δ[CO₂]nat, it can be estimated to be a sink (negative) of about half of what we emit. There is no other possibility. Knowing two of the variables gives you the third. Even if we consider unicorns’ farts, natural contribution is still a sink of about half the size of our emissions.

            As we have been in “lockdown” for some time and human emissions have decreased if IPCC were correct then a reduction in gradient of the Keeling Curve would be expected.

            That is also incorrect, sorry. According to the World Bank, the baseline forecast envisions a 5.2 percent contraction in global GDP in 2020. If we assume a 5 % decrease in emissions, instead of ~ 2.5 ppm we should emit ~ 2.38 ppm in 2020, if sinks remain the same the increase in atmospheric CO2 would be expected to be 1.19 ppm instead of 1.25. The difference is smaller than the annual variability by a factor of 5, which means it will not be noticeable. It would take many years to notice a 5 % reduction in emissions and we don’t know how sinks will respond to a reduction in the rate of our emissions. Will they also reduce their rate of change? Nobody knows.

            Friend Murry Salby is watching too.

            Murry Salby was shown to be wrong and if you want more evidence he said he was going to publish what he was telling at his talks, but he never did and he no longer says it. He was a sad case.
            Regards.

          • Just to check before I continue to disagree with you Javier. What is your best estimate for the residence time of CO2 in the atmosphere?

          • There are two separate issues regarding CO2 residence time that people usually confound.

            One thing is the residence time of a particular molecule of CO2 in the atmosphere. That time is relatively well known from studies with radioactive CO2 molecules from atomic bomb testing. It is just a few years. But that molecule is usually exchanged by another one from a different carbon cycle compartment.

            A different thing is the time required for a bulk release of new carbon from fossil fuels into the atmosphere to disappear. If we release 1000 Gtons of carbon to the atmosphere, how long will it take for them to disappear from the atmosphere? The answer to that is unknown, as a lot of assumptions go into any answer. It is generally believed that it may take centuries for 80 % of it to disappear and a lot more time for a complete removal, since it involves the slow carbon cycle through carbonate precipitation into sediments. I think this is not correct as the biosphere has a high capacity to soak up CO2, and it won’t release it for thousands of years.

          • Javier: You really know your IPCC stuff. The playbook reads something like as follows: Until the natural balance was upset by those evil fossil fuel burning Victorians and continued even more viciously by ourselves in the new Elizabethan period, the CO2 level was just under 300 ppm. Now with the overburden of all this accumulated CO2 from anthropogenic sources, even if we stop now at circa 400 ppm it will take a very long time to get back to the “natural level” of circa 300 ppm, hundreds, maybe thousands of years. Well actually the experiments on residence times show this is not the case. The range of residence times does not rely on experimental error but on genuine variability of natural emissions. From memory there were three major peaks in the chemical measured atmospheric carbon dioxide content 1820, 1855 and 1942. For example in 1930 the measured value was circa 330 ppm. By 1942 it was at 440 ppm and yet by 1950 the value was back again at circa 330 ppm. That’s a gain and a loss of 110 ppm in 20 years (Beck Energy & Environment 18: 259-282. One can argue that this is a location situation and does not represent the world with full mixing. However in terms of different sequestration processes that is the way things can work. Solubility in cold water is an extremely fast process. Whilst I would agree that subsequent “fixing” in carbonate rocks takes ages.

          • Javier is right that Dr. Salby is confused.

            Salby claims that atmospheric CO2 levels are rising, not because of anthropogenic CO2 emissions, but because global warming is causing the oceans to outgas CO2. It’s not, and they aren’t.
             

            The difference between the amount of anthropogenic CO2 emitted, and the amount by which CO2 level increases year-to-year, is the “CO2 removal rate.” That’s the rate at which negative feedback mechanisms, like terrestrial “greening” and dissolution into the oceans, remove CO2 from the atmosphere.

            The CO2 removal rate is affected by many factors, but mostly by the atmospheric CO2 level. Dr. Roy Spencer examined it, and found that it is closely approximated by a very simple function:

                (co2level – 295.1) × 0.0233
                (units are ppmv CO2)
             

            The “airborne fraction” (AF) is just the amount by which CO2 level increases year-to-year divided by the anthropogenic emission rate. It does not represent anything physically meaningful.

            The AF is sometimes inaccurately described as the portion of CO2 emissions which go into the atmosphere. That’s wrong, because ALL the CO2 emissions go into the atmosphere. Atmospheric CO2 is fungible, and little of the CO2 which is removed actually comes from that same year’s emissions.

            The AF is currently approximately 50%, but that’s just an accident of the fact that our current emissions happen to be about twice the removal rate. If our emissions were halved, the AF would drop to approximately zero.
             

            Peter F Gill asked Javier, “What is your best estimate for the residence time of CO2 in the atmosphere?”

            Because there are multiple processes removing CO2 from the atmosphere, at different rates, as well as processes which continually exchange carbon in the atmosphere for carbon in other reservoirs, there is no single “residence time” definition for atmospheric CO2. But here are three common definitions:

            1. The “effective residence time” or “adjustment time” is the definition which matters, for most purposes. It is the “e-folding time” for the effect on atmospheric CO2 level of CO2 added to the atmosphere by fossil fuels, cement manufacturing, etc. It is the time constant of the initial approximately-exponential decay curve which the atmospheric CO2 level would initially follow, if CO2 emissions were to suddenly cease.

            It is about fifty years. That’s about how long it would take for about 63% (1-(1/e)) of the anthropogenic increment to be removed. That makes the half-life (the time to remove the first half of the anthropogenic increment) about 35 years.

            The effective residence time is determined from measurements of atmospheric CO2 levels, and from economic data tabulating fossil fuel use and cement manufacturing.

            We have excellent records from which we can calculate, quite precisely, what the CO2 removal rate has been every year (since 1958), and we can tabulate that as a function of the same years’ annual average CO2 levels, from 315 ppmv (in 1958) to 413 ppmv (now). Then, since we know removal rate as a function of atmospheric CO2 level, we can calculate the effective residence time.

            2. The “molecular residence time” is the average amount of time that a particular carbon atom stays in the atmosphere. Since large amounts of carbon are continually being exchanged between the atmosphere and other reservoirs, this “residence time” is much shorter, and rather ill-defined.

            CO2 molecules often leave the atmosphere and then return to it. For example, CO2 dissolved in raindrops can return to the atmosphere when the resulting rain puddles evaporate, often in mere hours. Likewise, carbon taken from the atmosphere by grass in springtime returns to the atmosphere (albeit, bound to different oxygen atoms) in autumn, when the grass dies and decays.

            If you do not count carbon atoms as “removed” from the atmosphere when they’re removed but then the same atoms soon return to the atmosphere (as in the case of CO2 dissolved in an evaporating puddle of rainwater), then the molecular residence time can be closely estimated from the 14C “bomb spike.”

            When atmospheric tests of A-bombs and H-bombs suddenly ceased (following the atmospheric test ban treaty), the 14C concentration dropped on a near-perfect exponential decay curve, with a half-life of 11.5 years, implying a residence time of 16.6 years. You can see that in this log scale plot of the decline of 14C levels in the atmosphere, following the test ban:

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

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

            Note that 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 molecular residence time of 14CO2 are necessarily less than the “effective residence time” or “adjustment time” of CO2 emissions.

            3. The “full lifetime effect” residence time integrates the “long tail” of the hypothetical CO2 level decay curve, were CO2 emissions to cease. When climate activists claim that CO2’s atmospheric life time is very long (100 years or more), this is what they’re referring to.

            For example, Xiaochun Zhang & Ken Caldeira say that if you burn a lump of coal, then after the resulting CO2 has been in the atmosphere for 34 days, the total “greenhouse” warming effect from that CO2 on the planet will have equaled the warmth that you got from burning the coal; they further calculate that eventually, over its lifetime in the atmosphere, the CO2 will have a total “greenhouse” warming 100,000 thousand times greater than that. That means they are assuming a “residence time” of (34 days × 100,000) / 365.25 days/year
            = 9,309 years!

            That’s extreme, and certainly too long, but “full lifetime effect” residence time estimates much longer than fifty years are not necessarily wrong, they are just irrelevant.

            The main “negative feedback” processes which remove CO2 from the atmosphere are “greening” and dissolution into the oceans. CO2 removed from the atmosphere by these processes has not been returned to coal beds. Rather, it’s moved from the atmospheric carbon reservoir to the ocean’s carbon reservoir and the biosphere / soil reservoir, and it won’t stay there forever.

            That means that the hypothetical CO2 level decay curve, were anthropogenic CO2 emissions to suddenly cease, has a “long tail,” representing carbon from the biosphere / soil and oceans returning to the atmosphere, as atmospheric CO2 level falls toward 290 ppmv.

            In the case of the oceans, the carbon storage reservoir is vast, compared to the atmosphere, and calcifying coccolithophores transport carbonates from surface water, where the CO2 dissolves, to the ocean depths. So return of that carbon to the atmosphere would take a very, very long time, and some of it will never return.

            In the case of the biosphere / soil, the time would be shorter, because falling CO2 levels would cause a “browning” Earth, in which decay processes outstrip photosynthesis. But there’s no good reason to expect the carbon sequestered by “greening” (enlarging the biosphere) to return to the atmosphere, until CO2 levels are someday again very low.

            The hypothetical “long tail,” which so drastically exaggerates the Zhang / Caldeira “residence time” figure is not based on measurements. It represents modeled predictions of carbon theoretically released into the atmosphere from oceans and biosphere / soil in the distant future, when atmospheric CO2 levels are very low (well below 350 ppmv). But when CO2 levels are very low, the climate threat will be cooling rather than warming, and browning from CO2 starvation rather than greening from CO2 fertilization.

            Even if you accept the IPCC’s dubious claim that the next 0.5° or 1.0° of warming will be bad, there’s no denying the proven fact that the last 1°C of warming, and the ≈20% agricultural production boost from higher CO2 levels, were good. So when CO2 levels are very low, the release of CO2 from the biosphere / soils and oceans into the atmosphere will indisputably be a very good thing.

            Yet climate activists wants you to think it’s a bad thing. That’s just crazy talk.

          • You say quite a lot Dave and I will consider it carefully but I will not respond for some time for reasons already given elsewhere in this blog. I will say that those who have measured the CO2 residence time according to a different definition to any used by IPCC may or may not have known about any or all of the many sequestration mechanisms. This does not affect the determinations made. It does affect the interpretation of the results. I don’t think that there is general agreement on the latter. As regards the back AGW via the infrared absorption effects mentioned I would simply say that I am not a fan of the Trenberth diagram and in particular the implied heating effect of back radiation and in any event the contribution from CO2 is trivial compared to water vapour and other forms of water. We of course need more CO2 in the atmosphere not less and generally nature has been working against us on that one. I have few arguments with WG1 except of course that outrageously the people seem to meekly accept that the Summaries for Policymakers do not always reflect the science and in particular the uncertainties. I wonder given your response if Javier will bother responding.

          • Dave, I agree with most but not all:

            The AF is sometimes inaccurately described as the portion of CO2 emissions which go into the atmosphere. That’s wrong, because ALL the CO2 emissions go into the atmosphere.

            The AF is described as the portion of CO2 emissions that “remains” in the atmosphere. Although it is not physically correct, it is mathematically correct, and thus a useful concept.

            The AF is currently approximately 50%, but that’s just an accident of the fact that our current emissions happen to be about twice the removal rate. If our emissions were halved, the AF would drop to approximately zero.

            A huge assumption goes into that. We don’t know what would happen to the AF if we reduce our emissions because we have never reduced our emissions in a consistent manner. If both atmospheric levels and sinks respond to our emission levels, reducing our emissions might reduce sinks rate in which case AF wouldn’t change much.

            there is no single “residence time” definition for atmospheric CO2. But here are three common definitions:

            There’s actually two conceptual time references. As Freeman Dyson put it one is the time a molecule remains in the atmosphere until it is replaced by another molecule. This is usually calculated by dividing the total carbon of the atmosphere by the total size of the annual carbon fluxes to the land and ocean compartments. It is usually called (but not always) “residence time” and it is calculated at around 5 years. 14CO2 decay has a longer half life because a part of the radioactive molecules move out and back into the atmosphere before the half residence time is reached.

            The other one is the time it takes a molecule and all of its replacements to disappear from the atmosphere, so there is a molecule less. It is usually called (but not always) “adjustment time.” It is calculated using carbon cycle models and its half time goes from several decades to several centuries depending on the model, with the IPCC settling for 100 years. The adjustment time for a carbon pulse is believed to have a very long tail, so essentially after a carbon pulse it is believed that CO2 levels will remain elevated for millennia. Whether this is true or not nobody knows.

          • Javier wrote, “We don’t know what would happen to the AF if we reduce our emissions because we have never reduced our emissions in a consistent manner. If both atmospheric levels and sinks respond to our emission levels, reducing our emissions might reduce sinks rate in which case AF wouldn’t change much.”

            Not possible. There is no plausible mechanism through which any significant CO2 removal process could be affected by anthropogenic emission rates. The sinks all respond to atmospheric CO2 levels, not emission rates.

            “Greening” (CO2 uptake by the biosphere) is affected by CO2 levels. There’s no way for plants to detect or respond to emission rates, only to CO2 levels. Photosynthesis rates depend on the amount of CO2 in the air, not on the rate at which it goes up chimneys.
            http://sealevel.info/C3_and_C4_Pflanze_vs_CO2_Konzentration_2018.png

            The rate of CO2 absorption by water is likewise controlled by atmospheric CO2 partial pressure, not emission rate, per Henry’s Law.

            There is no possible mechanism through which removal rates could be significantly affected by emission rates.

          • There is no possible mechanism through which removal rates could be significantly affected by emission rates.

            Hypothetically there is. It is the reverse of what has happened over the past 70 years. As we have increased our emissions, atmospheric levels have increased and sinks have increased. If we reduce our emissions, atmospheric levels should decrease (because as you say sinks don’t respond to emissions), and sinks should therefore decrease too.

            Removal by sinks has increased as our emissions have raised atmospheric levels (maintaining AF near constant), and should decrease as our emissions decrease and cause a reduction in atmospheric levels.

            Whether this is so or not should await until we reduce our emissions and see what happens to atmospheric levels. They should first stall and then start decreasing.

          • Javier wrote, “If we reduce our emissions, atmospheric levels should decrease (because as you say sinks don’t respond to emissions), and sinks should therefore decrease too.”

            Agreed, but that’s a response to CO2 level, not a response to emission rate.

            Or if emissions plateau, then atmospheric levels will asymptotically approach a plateau, as well. It’s easy to calculate that approximate level, from the emission rate, using Roy’s formula:

                removalrate = (co2level – 295.1) × 0.0233

            The “plateau CO2 level” is the level at which the removal rate equals the emission rate, so:

                emissionrate = (co2level – 295.1) × 0.0233
                emissionrate / 0.0233 = (co2level – 295.1)
                co2level = (emissionrate / 0.0233) + 295.1

            So, if the net anthropogenic emission rate plateaus at 5 ppmv / year (approximately the current rate), then the CO2 level will plateau at approximately (5 / 0.0233) + 295.1 = 510 ppmv.

            Most climate activists claim that atmospheric CO2 levels will continue to climb as long as we continue to emit CO2. That’s utter nonsense.

            By the same formula you can calculate the sustained CO2 emission rate needed for CO2 concentration to approach a given target level. E.g., for CO2 levels to approach 725 ppmv would require sustained emissions at:

                (co2level – 295.1) × 0.0233 = (725 – 295.1) × 0.0233 = 10 ppmv/year

            Note that that’s approximately double the current emission rate.

            Thus we can say with assurance that if anthropogenic CO2 emissions never double from their current rate, then atmospheric CO2 levels will never reach 725 ppmv.

          • Dave,
            I did those calculations independently over two years ago for my article:
            https://judithcurry.com/2018/06/28/nature-unbound-ix-21st-century-climate-change/
            reaching the same value (510 ppm) through a different path:

            “The reason why sinks are taking up more CO2 from the atmosphere is that we are farther from equilibrium. Since atmospheric CO2 changed very slowly before anthropogenic emissions from fossil fuels, it can be assumed that sinks (K) and sources (S) were at equilibrium at 280 ppm (ΔK = ΔS). Due to warming the oceans release ~ 16 ppm/°C, so current equilibrium is ~ 290 ppm. Since the current level (~ 400 ppm) is above equilibrium level, sinks are larger than sources (ΔK > ΔS), and the the farther we are from equilibrium, the larger the difference between sinks and sources (ΔK–ΔS). If we stabilize emissions (E) near present levels, as current trend suggests, the difference between sinks and sources will continue increasing until it matches emissions (ΔK–ΔS = E), reaching a new equilibrium for constant emissions. Since we are ~ 120 ppm above equilibrium and sinks are absorbing 55% of our emissions (ΔK–ΔS = 0.55E), it can be calculated that for constant current emissions the new equilibrium lies at 220 ppm (120/0.55) above the present equilibrium value of 290 ppm, or 510 ppm.
            Given constant emissions at present levels, atmospheric CO2 should increase logarithmically towards 510 ppm, at which point sinks should match sources plus emissions (ΔK = ΔS + E).”

            Then we have the issue of limited fossil fuels. Supply side analysis indicates we shouldn’t go above 610 ppm by 2100, and a similar value is obtained from burning all proven reserves of fossil fuels. However, Peak Coal took place so far in 2013, and Peak Oil in 2018 which indicates we are growing very little (if at all) our consumption of fossil fuels. My estimate is that we will reach 500-550 ppm by 2100 at most. That automatically defuses alarmism. We cannot reach dangerous levels of CO2 if we don’t burn a lot more fossil fuels than we are currently burning, and we are not going to burn a lot more fossil fuels even if we ignore the climate issue.

          • Peter F Gill: ‘You say quite a lot Dave’. Yes, Dave Burton usually has a lot to say. Most of it, however, is hand waving, much like the IPCC.

            Anthropogenic fraction is a whimsical definition that is little more than circular reasoning. We postulate that there is no change of natural emission and removal of CO2, the dominant factors that control how much CO2 is in the atmosphere. Therefore, the additional CO2 in the atmosphere must be what remains from additional human emission… Brilliant.

          • Javier wrote, “I did those calculations independently over two years ago for my article… reaching the same value (510 ppm) through a different path”

            I’m glad to have been able to confirm your calculations.
             

            Ian wrote, “We postulate that there is no change of natural emission and removal of CO2, the dominant factors that control how much CO2 is in the atmosphere. Therefore, the additional CO2 in the atmosphere must be what remains from additional human emission…”

            What do you me, “we,” Kemosabe?

            Javier and I certainly do not “postulate that there is no change of natural emission and removal of CO2.”

            The natural net-removal rate of CO2 is increasing, as the CO2 level increases. As Javier correctly noted, “As we have increased our emissions, atmospheric levels have increased and sinks have increased.”

            But that isn’t how we know that anthropogenic emissions are responsible for rising atmospheric CO2 levels. We know that because we have the measurements of atmospheric CO2 levels, and thus of the year-to-year changes in those levels, and we know the rate of emissions have the tabulated economic data about fossil fuel use and cement manufacturing. Since the latter has been greater than the former, every year since 1958, we know that nature is removing CO2 from the atmosphere each year, rather than adding it. Furthermore, the difference between those two figures has been generally increasing — just as you’d expect, from Henry’s Law, and from plant responses to CO2 fertilization.

          • Dave Burton
            “Note that 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. ”

            I assume that this is an isotope swapping effect due to differences in atomic mass?
            If so does a similar isotope switch occur between C13 and C12?

          • Philip asked, “I assume that this is an isotope swapping effect due to differences in atomic mass?”

            No, it’s the effect of random exchanges.

            Suppose you have two piles of pennies, one larger than the other. The small pile is 10% copper pennies (pre-1982) and 90% zinc (new) pennies. The larger pile is only 1% copper pennies, and 99% zinc.

            You grab a handful of pennies from each pile, and drop each handful into the opposite pile. (Let’s assume your “handfuls” each hold exactly the same number of pennies.) What effect does that exchange have on the composition of the two piles?

            After you’ve done the exchange, each pile contain the same amount of money that it started with. But the composition of the small pile is now less than 10% copper pennies, and the big pile now has more than 1% copper pennies.

            Now, as it happens, zinc pennies weigh less than copper pennies. The density difference might slightly bias which pennies you happen to get, when you grab your handfuls. My guess is that heavier pennies might slip through your fingers slightly more readily. So perhaps the handful you got from then “10% copper” pile is only 9.8% copper pennies, and the handful you got from the “1% copper” pile is only 0.98% copper pennies.

            That bias will very slightly change the effect that your exchange operation has on the composition of the two piles. But not much.

            Similarly, the mass difference between 12CO2, 13CO2 & 14CO2 does have a slight effect on the rates of various biological and chemical processes. But not much.

      • Peter,
        “IPCC also use a misleading argument about the ratio of C12 /C13 to support its failing hypotheses.”
        I would love to hear a robust dismissal of the C12/C13 ratio argument.
        This particular canard has been running for far too long and needs to be quashed.

        • Hi Philip: Here is perhaps not the best place for a “robust” response on the isotopes question. However, I shall give some thoughts on the matter. Firstly I recall discussing this with Dick Lindzen. We agreed that there is insufficient recognition and characterisation of CO2 sources and sinks. This having been said we do know that the various known sources and sinks behave differently. When sea out gassing is a major factor then Henry’s Law means that any increase of the partial pressure by other unstoppable sources like fossil fuel burning, vegetation decay etc will have the effect of suppressing what would otherwise have been emitted from the seas. This means that the balance of C12/C13 will be displaced in favour of C12. As regards C14 and forgetting its decay back to nitrogen, a similar argument with respect to C13 exists for plants i.e plants appear to prefer C12. However, the preference is small and plants love C in any of its isotopes. Incidentally some time ago I came across a paper that claimed that shell making organisms prefer C13 for their shells but I lost the reference and despite my best efforts my searches for that paper have failed. The other objection to the C12/C13 argument related to the nature of CO2 emitted from the sea floor and from land based volcanoes. I guess this to a large extent relates to the release of CO2 from carbonates from the distant past when past C12/C13 atmospheric ratios were different and variable. Of course in many ways this whole subject is a distraction, as clearly anthropogenic emissions play a negligible part in climate change and indeed changing atmospheric CO2 is generally an indicator of climatic change rather than its cause.

          • Hi Peter,
            Thank you.

            “This means that the balance of C12/C13 will be displaced in favour of C12.”
            As indeed we would expect, the lighter C12 isotope is “expressed” from the water into the air more often.

            “shell making organisms prefer C13 for their shells ”
            Same point, the heavier C13 isotope “settles” into the crystal structure more readily.

            Given both of these points the isotope ratio standard from the marine Pee Dee Belemnite does not represent the liquid seawater ratio and certainly not the surface out gassing ratio.

            “Of course in many ways this whole subject is a distraction”
            Sadly, to distract is the whole point.

    • Is there some data, calculation, or logic error in that conclusion

      Perhaps you are assuming that Scripps measurements can be extrapolated to a global ocean CO2 change.

      CO2 in seawater is dependent on many factors and some of them act locally. Measurements are too sparse to calculate a global average that can be followed over time.

    • Clearly I have not stated my question coherently. The question is
      Does the measured increase in ocean content CO2 (from 1958 to 2014) really equal MANY times the TOTAL human emissions over the same time period?
      Or is there some fault with either the measurements or the calculations that produce that many times number?

      This seems to be an observational fact (or fiction) quite independent of ANY theory about the effects of human emissions.

      • No way, Andy. The fluxes into and out of the ocean are very large, of the order of 150 Gt/year, but the net balance is much smaller. For example for the year 2000 the net flux was calculated at 1.4 Gt carbon from the atmosphere into the ocean. That year human emissions amounted to 7 Gt carbon. About 3.5 remained in the atmosphere, 1.4 went into the ocean and 2.1 into land.
        https://worldoceanreview.com/en/wor-1/ocean-chemistry/co2-reservoir/

        The source of Chaamjamal is an article that was never published, but placed in a preprint repository in 2015 and never cited by anybody. I would be suspicious of anything it says without independent confirmation, and the hypothesis of the article is wrong. Ocean CO2 changes should follow atmospheric CO2 changes, not emissions. How could the ocean know how much we emit?

        • Javier wrote, “Ocean CO2 changes should follow atmospheric CO2 changes, not emissions. How could the ocean know how much we emit?”

          Exactly right.

        • The hypothesis expressed is that the CO2 source is under the ocean. The reason, right or wrong, is that the increase in ocean CO2 far exceeded total human emissions. Since the atmosphere CO2 increase was about 1/2 of human emissions, if the ocean concentration was indeed so much larger, most of its CO2 increase could not have come from the atmosphere — unless there is some reason to believe a tremendous quantity of CO2 comes from somewhere then disappears into the ocean too fast to show up in any atmospheric measurements.

          We do know there are ocean geothermal CO2 sources and, in some places, those sources lead to very much higher local ocean CO2 concentrations than those measured by Scripps Institution of Oceanography. What is missing is an indication of whether or not the Scripps measurements are indicative of the ocean in general or just some limited location(s).

          • The reason, right or wrong, is that the increase in ocean CO2 far exceeded total human emissions.

            I’d like to see the evidence for that, and I am not about to trust what Chamjamaal or his source say about it. With the increase in atmospheric CO2 levels the oceans are taking more CO2 from the atmosphere and that displaces the DIC (dissolved inorganic carbon) equations towards consuming CO2 and producing carbonates and bicarbonates, so the oceans are not producing CO2, they are storing a bigger amount that comes from the atmosphere. Due to very limited mixing, the deep ocean, which is by far the biggest carbon store, has not been affected so far by our CO2 activities.

            Tectonic sources of CO2 are very small. Even if we thought that underwater volcanoes are 20 times surface volcanoes, their contribution to CO2 levels would still be too small.

  9. The professor has released a copy of his document to Rud, for peer review. He is obviously looking for feedback so Rud, please forward this to him.

    I downloaded the document (free of charge) from:
    https://www.academia.edu/43859654/Algorithms_in_Ocean_Chemistry

    My mother always used to tell me “if you can’t say anything decent, say nothing”, so let me start by saying that I enjoyed it and learned from it, even though the finer points of the chemical processes escaped me. Notwithstanding, I’ll must make a couple of observations about the (sixty page) document. It’s always hard to present a review in writing. One’s words can be read as terribly negative. I don’t mean this to sound as if I’m panning the work. I’m not.

    OK, the document describes itself as a “handbook” (Sec 3.7). For me, the term “handbook” leads me to expect a description of steps and the sequence in which they are to be performed. More importantly, it leads\ me to expect a description of how to use the code that comprises the last nine pages of the document. Or better still, a worked example.

    Unfortunately, we don’t get that. What we get is (to me) a disconnected set of “chemical concepts”. That leads me to my main concern – exactly at whom is this document aimed? Is it aimed at academic chemists who may be interested in climate change? Or is it aimed at climate change researchers who want to know something about the underlying chemistry of CO2 in the oceans? I think that if the author made up his mind about who – exactly – constituted the target audience, and edited the paper with them in mind, the document would be more effective.

    From an “English essay” aspect, the document needs cleaning up. It reads as if it was a “stream of consciousness” first draft of the words, with the actual chemical reactions added on the second pass. There are several instances where the words almost seem to act as place markers for additional text or explanation to be added, but for which the extra text is still missing. Eg:

    • “The code is self-explanatory to some extent” (Sec 3.6) (So add more comments to the code or add a separate description.)

    • “The standard seawater composition as listed may be supersaturated with respect to calcite or aragonite formation. Calcite is the less soluble form of calcium carbonate, so theoretically it should be the first to precipitate. Coral reef is however made up of aragonite, a fact that should be considered.” (Sec 4.3) (And the effect of that is, what?)

    • “the algorithms employed only assume the effect of water column pressure, so on the sea surface itself the pressure is assumed to be zero. This is unrealistic, as it neglects air pressure being nearly equal to 1 atm at sea level, but should be used as the empiric algorithms assume so.” (Sec 4.4) (And the effect of that is, what?)

    • “CO2 Partial Pressure and Fugacity” (Sec 5.1 – which cries out for an explanation of the difference between the two – not just how “Fugacity” is mathematically derived from Partial Pressure.)

    • “For more insight see Section … (kinetic)” (Sec 6.2 Para 3 [Presumably should be “Chapter 2. Kinetic Systems”)

    However, my main criticism is not of the paper, but of the code.
    It is only 600 lines long, and it is really simple (commented!) BASIC code, but what we see in it is the epitome of computer coding carried out by amateurs.

    If you can, look at some serious industrial code.
    Look at the revision history. For each version: who changed it, why, and which sections.
    Serious industrial code is kept in a code repository. The maintenance programmer books it out and books it in after maintenance, testing and release approval.
    What we see with this code is how certain epidemiologists try to maintain 15,000 line programs – nothing in it to say what version you’re looking at – good luck knowing what’s changed in the last six months!

    So I invite the professor to talk to some professionals – outside his university – find out about code management and ensure when he releases the next draft of his paper he shows evidence of professional source control.

    But as I said, I spent a few hours working through the paper, and I enjoyed it.

  10. The marine biological carbon pump
    https://www.rapid.ac.uk/abc/bg/bcp.php
    What is the biological carbon pump?
    Just like plants on land, the microscopic marine phytoplankton take up carbon dioxide [CO2] and water [H2O] from their surrounding and use energy from sunlight to turn it into glucose [C6H12] and oxygen [O2]. The glucose powers the metabolism of the plankton cells, and can be turned into other organic compounds. If enough nutrients are available the plankton will grow and multiply.
    Phytoplankton are the ‘grass of the sea’ – at the bottom of the marine food chain. Respiration by animals, bacteria and plants ‘remineralises’ the organic carbon – turning it back into carbon dioxide and water.
    When plants and animals die their remains sink into deeper water as detritus and decompose, releasing carbon dioxide and nutrients back into the water. This is why nutrients such as nitrate are scarce in surface water, but found in much higher concentrations in the deep ocean.
    The transformation of carbon dioxide and nutrients into organic carbon, its sinking into the in the deep ocean, and its decomposition at depth, is known as the biological carbon pump. It contributes to the ocean’s uptake and storage of carbon dioxide and keeps atmospheric CO2 about 200 ppm lower than it would be if the ocean were without life.

  11. The biological carbon pump. “It contributes to the ocean’s uptake and storage of carbon dioxide and keeps atmospheric CO2 about 200 ppm lower than it would be if the ocean were without life.”
    This is really significant estimates. Surprising that it never got the attention it deserves.

    • Phytoplankton never get the attention they deserve.

      Onto the bigger question upthread: why chemists and physicists tend to ignore complex biological systems. As a marine biologist I can tell you, there are too many variables and too many uncertainties. I’ve seen more people drop out of biology programs and coached more through basic Bio 101 that turned out to be brilliant in chemistry and physics but could not wrap their heads around recombinent DNA because there are too many variables.

      Biology is the most complex science and all aspects of it–including medical–is riddled with uncertainty and extremely large variations and variables. For some, that is just too much uncertainty.

    • Thank you fore some clarification Just Jenn. I think the carbon cycle of oceans is important.
      From Woods Hole Oceanographic Institution
      The ocean’s ‘biological pump’ captures more carbon than expected
      “Scientists have long known that the ocean plays an essential role in capturing carbon from the atmosphere, but a new study from Woods Hole Oceanographic Institution (WHOI) shows that the efficiency of the ocean’s “biological carbon pump” has been drastically underestimated, with implications for future climate assessments.
      In a paper published April 6 in Proceedings of the National Academy of Sciences, WHOI geochemist Ken Buesseler and colleagues demonstrated that the depth of the sunlit area where photosynthesis occurs varies significantly throughout the ocean. This matters because the phytoplankton’s ability to take up carbon depends on amount of sunlight that’s able to penetrate the ocean’s upper layer. By taking account of the depth of the euphotic, or sunlit zone, the authors found that about twice as much carbon sinks into the ocean per year than previously estimated”

      • Depth of the photo zone depends on more than just some variables, it depends on a ton, latitude being the biggest, fauna next, mid level currents, halocline, thermocline….and the list goes on.

        The biggest problem facing ocean research is the cost to do that research on a boat. Most of the research conducted is near shore with 1-2 day excursions, maybe a week at the most expensive and usually conducted during the months of the least activity in the oceans due to safety of the boat, crew, and researchers. A gale force 3 can scrap a research trip depending on where that trip was to take place.

        Given that we have a limited scope on things, it is no wonder that we know less about the mid level ocean than we do about Mars. Our sampling of the ocean water column is pretty dang small in comparison to the scope and scale. As for twice as much carbon sinks per year than previously estimated–that may be true for that particular spot and you can extrapolate for similar conditions at that latitude, but you can’t conceivably say for the whole ocean.

        There was an intriguing hypothesis in the 90’s about carbolic acid–not as a climate change thing, it was being studied for the acquisition of zooplankton in coral. They posited that given the desert conditions on most coral reefs, the carbon had to come from the cooler richer waters to the north and south, and also posited that an unknown mid level current system may be bringing vital minerals to reef systems unbeknownst to anyone. To my knowledge they either didn’t receive funding—either because it didn’t include El Nino (hot topic at the time), CAGW (hadn’t fully formed yet into man’s wastefulness of the Earth), or because it would require them spending almost a year at sea to study how changing seasons changed the nutrients flowing to the major then known coral reefs. I dunno but it was a very intriguing idea all the same.

  12. Nice essay as usual, Rud.
    FYI typo: Whiskey Creek hatchery has othing to do with CO2 emissions and ‘ocean acidification’.

    • YAh. One of several typos I sent in a late revision to Charles after realizing and phoning him that my crucial early Mazza hyperlink was dead. He fixed the link without using my later sent him own typo fixed Link plus some more minor edits. Got version control proofs. My bad only.
      Happens when you all pay us nothing. I will strive to do better next post, whenever.

  13. Finished the paper.

    Overall I found it to be a fascinating read and it answered several questions I have wondered about for years, and answered some questions I only had for minutes!

    I have only one request – the section “8.4 Contributions to CO2 Absorption by Fresh Waters” seemed to just kind of end without a proper conclusion or summation. I am not sure why its even in there as it appears to just dangle.

    Some questions that hit me are: “Is land use impacting the calcium carbonate dissolution rate of fresh waters?”. It seems like it should, but I don’t have a feel for how much or is it enough to be important? Also, if the global temperature (whatever that really is) is increasing, shouldn’t water be able to dissolve calcium carbonate faster? (but the actual total amount the water can carry would be less). If global warming leads to more rainfall, would that also increase dissolution rates?

    I would love to see more on the Fresh Water section as I never see that addressed anywhere else.

    • “I have only one request – the section “8.4 Contributions to CO2 Absorption by Fresh Waters” seemed to just kind of end without a proper conclusion or summation. I am not sure why its even in there as it appears to just dangle. ”

      Robert,
      I think the reason for this is that Daniele Mazza has reached the boundary of two vast fields of geochemical knowledge, namely Diagenesis (the alteration of rock crystals) and Pedology (the formation of soils).

      The key point is that although it is well understood that the solution of limestone and dolomite (calcium and magnesium carbonates) by rainwater that is naturally acidic (because it contains dissolved CO2) is a key process in returning carbonate ions to the ocean, that is only part of the story. The base metal cations of calcium and magnesium that form these carbonate precipitate rocks are themselves derived from the earlier chemical weathering of basaltic rocks by acidic rainwater and humic acids. Basalts which as the name suggests are those igneous rocks that contain base metals.

      This diagenic process that creates from basic igneous rocks silica sand, clay minerals and soluble salts, which has progressed throughout all of geologic time, is the reason why the sea contains, sodium chloride in solution and a buffered reservoir of calcium, magnesium and carbonate ions. Adding weak carbonic acid solution to alkaline seawater therefore is not and never will be “ocean acidification”

  14. Chapter 5 of my site (click my name) discusses and shows how to calculate ocean’s pH accurately. That difficult for you and so the Table shows what possible CO2 levels may generate; there’s nothing to worry about. It’s standard acid/base equilibria as taught in 1st year uni chemistry but why are such discussions but not results published?

Comments are closed.