Correcting Misinformation on Atmospheric Carbon Dioxide

Written by Bud Bromley on May 25, 2022. Posted in Current News

Digital signal processing technology was used to analyze daily carbon dioxide data from NOAA’s Global Monitoring Laboratory.

The period surrounding the 1991 eruption of the Pinatubo volcano was rigorously analyzed for slope and acceleration of net global average atmospheric CO₂ concentration and found to be consistent with the theory that Henry’s Law, the Law of Mass Action, and Le Chatelier’s principle control net global average atmospheric CO₂ concentration rather than human-produced CO₂ emissions.  Background and theory are explained.

A method of using common physics and math for a novel purpose is presented to compare natural CO₂ emission or absorption with human-produced CO₂ emission.  The claim that human-produced CO₂ emission is causing increasing global CO₂ concentration and climate change is shown to be without scientific merit.

William Henry tested and documented his series of experiments on different gas and liquid combinations under various conditions which were published in 1803. (Henry, W., 1803) Today, the coefficients he developed are now available in tables in reference books and software which are used routinely by chemists and chemical engineers. This stable science is known today as Henry’s Law and is a foundation science for several large industries.

Though it is not common knowledge among the public and only rarely found in climatology literature, Henry’s Law is the foundation science for the multi-billion dollar per year scientific instrumentation industry of gas chromatography, which is one of the methods used to measure atmospheric gases and most chemicals.

It is also a foundation science underlying chemical engineering in gas, oil and coal refining and the beer and carbonated beverage industries. Also, it is one of the major variables in the absorption and emission exchanges of oxygen and carbon dioxide and other gases in the lungs and gills of all animals.

The event and its causes and effects are the subjects of many studies, for example, Stenchikov et al, 2021.

An excerpt from Science News at the time (Hoppe, 1992):

Ellsworth G. Dutton, a meteorologist with NOAA’s Climate Monitoring and Diagnostics Laboratory in Boulder, Colo., traced the effects of Pinatubo’s cloud with ground-based instruments that directly measure the strength of sunlight. Dutton says his results show a 20 to 30 percent decline in the amount of solar radiation that reaches the ground without being scattered or reflected, and a 2 to 4 percent decline in total solar radiation.

Temperatures have already started to drop, both at ground level and in the lower atmosphere, says James K. Angell of NOAA in Silver Spring, Md. Angell told Science News his analyses of weather balloon data show that the first half of 1992 was 0.4 [degrees] C cooler, overall, than the first half of 1991. He notes that the volcano’s effect may be greater than suggested by these observed temperature shifts, since this year’s El Nino warming would normally raise average temperatures by 0.2 [degrees] C (SN: 1/18/92, p.37).

Weather satellites confirm cooling in the lower atmosphere, recording a global drop of more than 0.5 [degrees[ C since last June, with this June being 0.2 [degrees] C cooler than average, according to John Christy of the University of Alabama at Huntsville and Roy Spencer of NASA’s Earth Science Lab at the Marshall Space Flight Center in Huntsville.

Christy says their data indicate that the greatest cooling, 1.0 [degrees] C, occurred in the northern midlatitudes — an area that includes the continental United States — while temperatures in the southern hemisphere have dropped by only 0.3 [degrees] C.

https://en.wikipedia.org/wiki/File:Mauna_Loa_atmospheric_transmission.png

Pinatubo was the largest or second largest volcanic explosion observed on Earth in the last 100 years.  The explosion resulted in a belt of clouds, dust, various gases, and particles encircling and spreading in the atmosphere around Earth’s tropical zone, which is about 20 degrees latitude both north and south of the equator.  In this large zone, ocean surface temperature averages 25 C (77 F) year-round, in contrast to average ocean temperature of 17 C.

On average, ocean surface above 25 C is a net emitter of CO₂ gas, day and night, year-round.  That is, more CO₂ is being released from ocean surface than is absorbed from among the CO₂ molecules which are continuously colliding with ocean surface.  The belt of clouds, gases, and particles, etc., encircling the tropics is assumed by all known reports to have reduced short wave solar insolation reaching the surface; incoming sun light around 400 to 700 nanometer wavelength was shaded, blocked, absorbed, reflected, scattered, or otherwise obfuscated.  Consequently, tropical ocean surface cooled.  Higher latitude ocean surface cooled also.

Short wave infrared radiation from the sun is not absorbed by CO₂. It is absorbed by ocean, soil, and biosphere. 

Our theory is that Henry’s Law controls net global average atmospheric CO₂ concentration and human CO₂ emission from all sources only temporarily perturbs net global average atmospheric CO₂ concentration and its rate of change.  There are other science groups and individuals who support this theory.  But this theory is rarely studied or found in climate literature and rarely funded in government environmental work.  Generally, papers concerning Henry’s Law and climate are found only in less well-known journals.

Henry’s Law is a reproducible, well-documented law of chemistry and physics which defines the ratio of any gas in contact with any liquid.  Each gas and liquid combination has a specific Henry’s Law coefficient, denoted k_H.   The coefficient is not a constant; k_H varies with temperature at the gas – liquid interchange surface.

The coefficient varies with (a) temperature of the surface (b) salinity of the liquid including certain minerals which are dissolved in the liquid not only sodium chloride, (c) alkalinity or pH or the liquid, (d) partial pressure of the gas in the space above the liquid and (e) partial pressure of the gas in the liquid.  Concentration of CO₂ gas in seawater is inversely proportional to sea surface temperature.  High diligence is needed in sampling procedures to control (a), (b), (c), (d) and (e).

Henry’s Law has limitations on its application.

1. Henry’s Law only applies when the concentration of the unreacted gas in the liquid is minor and when the concentration of gas being measured in the gas volume above the liquid (i.e., its partial pressure) is minor relative to the other gases in the volume.  An oversaturation condition is observed in chromatography by an abnormal, non-Gaussian peak shape.  Henry’s Law is applicable to CO₂ gas since it is a trace gas in both the atmosphere and in the ocean even at 10 times current concentrations.

2. Henry’s Law only applies to the gas in the liquid which has not reacted with the liquid; that is, Henry’s Law only applies to the reversible phase-state equilibrium reaction [CO₂(gas)] <-> aqueous [CO₂(gas)].  Henry’s Law does not apply to ionized CO₂ gas, that is, hydrated CO₂, nor to any of the carbonate or bicarbonate ions or un-ionized carbonic acid that are products of aqueous CO₂ gas reacting with water known collectively as dissolved inorganic carbon (DIC).

The total concentration of dissolved inorganic carbon is: (Cohen and Happer, 2015)

                                   [C] = [CO₂] + [HCO^{− 3}] + [CO₂^{− 3}]

Most of the CO₂ in seawater is in DIC form, which, according to most sources, is on the order of estimated 38,000 gigatonnes (Gt) of DIC dissolved or reacted CO₂ in deep seawater. Meanwhile 1000 Gt is in surface seawater and 850 Gt in air. (One Gt is 1000 billion kilograms, that is, 1 followed by 12 zeros.)  Figure 2 in Cohen and Happer (2015) illustrate the relative molar stoichiometric concentrations of the DIC species in ocean corresponding to atmospheric CO₂ concentration.

Barely visible, the fine dotted green line slightly above the horizontal axis is increasing. The concentration of the CO₂ species of DIC in ocean and the concentration of the bicarbonate species in ocean are both increasing as atmospheric CO₂ concentration increases.  Simultaneously, the carbonate ion [CO₂^{− 3}] of carbonic acid is decreasing, along with alleged problems of so-called “ocean acidification.”

As we demonstrate in this paper, CO₂ gas is rapidly absorbed into sea surface when the surface cools.  Ocean surface demonstrates the capacity to rapidly absorb orders of magnitude more CO₂ than humans produce, and then recover to trend. It is imperative to recognize that these reactions of ionized CO₂ (DIC) are rapidly reversible reactions. We do not rely on estimates of models of CO₂ in air and seawater to demonstrate this point.

Most CO₂ in seawater is in the ionized form HCO₃^– known as bicarbonate as shown in the Happer and Cohen figure 2 above.  Minor changes in ocean surface temperature reverse the CO₂ hydration reaction and aqueous CO₂ gas is formed.  Aqueous CO₂(gas) <-> H⁺ + HCO₃^–. Colder water pushes this reaction to the right.  Warmer water pushes the reaction to the left. Once in its aqueous CO₂ gas form, then Henry’s Law dynamic equilibrium applies: for a given seawater surface temperature, there is a fixed ratio of CO₂ gas concentration in air versus CO₂ gas concentration in seawater surface which is in contact with the air.

Depending on changes in surface conditions, aqueous CO₂ gas could react with H₂O to become H₂CO₃(carbonic acid), or it could react with H₂O to become HCO₃^– (bicarbonate) plus hydrogen ion (hydronium), or it could remain in the water matrix as aqueous CO₂ gas, or it could be emitted to the atmosphere as CO₂ gas.

Cohen and Happer (2015) explain that transition of only a single proton (a hydrogen ion), determines bicarbonate versus carbonic acid species.  The various DIC species are surrounded in the seawater matrix by hydrogen ions and hydroxide ions.  CO₂ gas molecules and DIC ions are not required to move in the seawater matrix.  Both bicarbonate ion and carbonic acid are separate reaction products of the aqueous CO₂ gas hydration reaction with H₂O, as well as reversible with each other, as shown in the next graphic.

In seawater surface these reactions can reverse in seconds due to changing surface temperature, or agitation by waves, buoys and moving ships, or a sampling procedure, or by an upwelling water current dense with DIC (e.g., an El Nino current).  As upwelling seawater dense with DIC comes to the surface, it warms, and aqueous CO₂ gas in the surface becomes oversaturated, out of balance with the Henry’s Law ratio for the temperature at the surface, resulting in CO₂ gas being emitted to the air and a rebalancing the Henry’s Law dynamic equilibrium for that temperature.

Daniel Mazza explains on pages 16 and 17, Reversible Reactions of Higher Order. (Mazza, Daniele, 2020)

 At any given temperature, the value of Keq remains constant no matter whether you start with A and B, or C and D, and regardless of the proportions in which they are mixed. Keq varies with temperature because k1, and k2 vary with temperature, but not by exactly the same amount.

… the general formulation of the law of mass action (Guldberg-Waage, 1864) that states: in a chemical system at equilibrium and constant temperature, the ratio between the product of the concentrations of chemicals formed (each elevated to its stoichiometric coefficient) and that of the reagents is a constant value.

The reactants and products of the carbonate chemistry in seawater are difficult to sample and quantify with precision because the reactions are so rapid and only very minor changes in surface conditions are required to change the dynamic equilibrium. Taking a sample affects the reactions.

Special methods and systems must be used for these analyses at the thin layer at ocean surface.  Journal and online articles report years or hundreds of years are required to move large amounts of CO₂, allegedly because migration of CO₂ vertically or horizontally in the water matrix is slow.

There are such slow changes, with El Ninos and La Ninas being prime examples.  However, simultaneously, second by second, bulk CO₂ gas is continuously in flux into and out of millions of square kilometers of ocean surface, driven by SST change and CO₂ is converting in seconds from one ionic species to another and aqueous CO₂ gas is either released to air or hydrated to carbonic acid or bicarbonate.

Slower or continuous changes such as human emissions are anomalous perturbations to the trend of the dynamic equilibrium for the local surface temperature.  Adding or subtracting CO₂ from any source or for any residence time or emission rate results in reset of the concentrations in the Henry’s ratio for a given temperature.

Demonstrating an example of this bulk sea surface reaction and its enormous quantity and rate in the natural environment as observed in the Mauna Loa data is a primary objective of this study.

The cyclical hydration reaction of aqueous CO₂ gas with H₂O is described in the following graphic:

Changes in kinetics force the reactions forward or backward, changes in kinetics are changes in motion of molecules.  Those kinetic changes result from heating, cooling or agitation of the sea surface by waves, ships underway and buoy motion, currents, storms, gas and water sampling procedures, etc.  For example, warm tropical sea surface that is normally continuously emitting CO₂ gas can be depleted of CO₂ gas by wind, storms, hurricanes, typhoons, etc. such that the undersaturated sea surface is absorbing CO₂ from air instead of emitting.

Significant sampling problems in actual sea water include CO₂ gas added or subtracted by the biology – living and dead – in the sea, currents of CO₂ dense seawater upwelling from deep ocean to the surface, and sampling sea surface when the necessary representative sample is only the top centimeter or less thin layer.

Simultaneously with the portion of the carbonate chemistry described above, calcium ions (Ca²⁺),which are readily available in seawater in great excess to carbon, react with bicarbonate ions (HCO₃^–) producing calcium carbonate (CaCO₃).  This reaction is not included in the Henry’s Law equilibrium, and not included in the estimated 38,000 Gt of DIC, and not included in the estimated 1000 Gt of DIC in sea surface, although it is accumulated inversely proportional to temperature into the largest CO₂ sink by orders of magnitude.

As Richard E. Zeebe and Dieter A. Wolf-Gladrow remind us, aqueous CO₂ gas as well as solid precipitant calcium carbonate are produced, “at surface water conditions… counterintuitively.. during CaCO₃ precipitation CO₂ is liberated…by only ~0.03 µmol per µmol CaCO₃ precipitated.” (Zeebe and Wolf-Gladrow) The famous white cliffs of Dover and Sussex, England, limestone caves around the world, the famous marble quarries of Italy are examples of enormous CaCO₃ deposits.

Ultimately, when the Henry’s ratio for CO₂ is out of balance, the DIC and Ca²⁺ reactions move to the right, towards products and excess CO₂ in converted to rock.  The calcium reaction is another source of CO₂ in sea water while at the same time it removes bicarbonate.

Ca²⁺ + 2HCO₃^– -> CaCO₃ + CO₂ + H₂O

CO₂ gas dissolved in ocean surface is estimated to be 30 to 40 times more concentrated than in air, results from multiple reactions, yet still a minor component of sea surface water.  But this estimate is many meters of ocean surface.  In this report, we are concerned with the CO2 in the thin layer at the sea-air interface.  This report and project do not rely on estimates of CO₂ concentration.  Demonstrating measurements of  CO₂ absorption and emission and their rates in comparison to human emissions is the purpose of this project.

This is taken from a long document. Read the rest here: budbromley

Bold emphasis added

Header image: UCAR

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