The Physics & Chemistry of Carbon Dioxide Formation, Absorption, Gasification and Transport in the Earth’s Atmosphere & Hydrosphere

Abstract

The total amount of carbon dioxide in the atmosphere is independent of biogenic and anthropogenic CO₂ generation and primarily dependent on temperature gradients on the surface of the oceans. The Earth’s atmosphere contains a trace amount of CO₂ at 0.04% in a gaseous mixture of predominately nitrogen, oxygen, and argon. All life forms on Earth are carbon based. Plants acquire their carbon from gaseous carbon dioxide or CO₂ in the atmosphere and convert it to plant cells through photosynthesis. Mammals acquire their carbon by eating plants. Biogenic carbon dioxide is produced naturally by animals, bacteria and the decomposition of organic matter some of which may be deeply sequestered underground and gradually vented. Additional natural CO₂ is released into the atmosphere by volcanic activity much of which occurs under deep ocean waters. Anthropogenic CO₂ is produced by the use of hydrocarbon fuels and the production of cement. All free or non-contained CO₂ on Earth is contained in the hydrosphere or atmosphere in a temperature dependent ratio of approximately 50:1 controlled by Henry’s Law. Additional quantities of CO₂ combine with other chemicals primarily in the Earth’s oceans forming stable chemicals governed by Raoult’s law as altered by non-ideal solutions. These fundamental laws of physics and chemistry control the total amount of CO₂ in the atmosphere in real time and falsify the incorrect but often cited “residency time” of atmospheric CO₂. The controlling predominate factor of the relative percentage of anthropogenic CO₂ in the total atmospheric reservoir of CO₂ is Henry’s law and its partition ratio. CO₂ is CO₂ and the atmosphere treats all sources of CO₂ the same regardless of the carbon’s isotope and source.

Key Words:

Atmosphere, hydrosphere, headspace, Henry’s law, solubility, aqueous CO ₂, carbonates, pH, CO₂ flux, signal to noise ratio, biogenic, anthropogenic

Introduction

Since the famous “Exxon Knew” paper of 1957 (Humble Oil Company, Brannon, Daughtry, Perry, Whitaker, & Williams) the preponderance of journal papers, common literature, media reports and websites from NASA to NOAA lead their discussions and presentation concerning the unproven hypothesis of AGW/climate change with the assertion that CO₂ resulting from man’s use of hydrocarbon fuels along with the production of cement contribute materially to the warming of the Earth due to greenhouse gas emissions. They follow this with various theories suggesting that four molecules of CO₂ per every 10,000 molecules of N, O, and Ar combined in the lower troposphere, directs reradiated heat to the Earth and creates global warming or climate change.

However none of these papers, articles, media reports and websites has provided one iota of empirical evidence that CO₂ is, in fact, responsible for any “increased warming” on the Earth.

The inference is that the increase in total atmospheric CO₂ concentration as displayed by the Mauna Loa Hawaii Keeling curve of 94 parts per million (0.0094%) over the last fifty years results totally from man’s use of hydrocarbon fuels and production of cement, and that this, in turn, creates warming; but again there is no empirical evidence to support either assertion. Nor has there been any empirically measured and calculated proof of the actual amount of anthropogenic CO₂ contained in the atmosphere.

Various supportive and adversarial rebuttals have been offered based on attempts to calculate and measure equilibriums in the Earth’s carbon budget and CO₂ production. However these efforts all produce misleading results.

Calculating the mass or volume of fossil fuel carbon dioxide emissions as a percentage of the estimated mass or volume of atmosphere (or estimated volume of mass of atmospheric CO₂) is not equivalent to the amount of fossil fuel CO₂ in the atmosphere. Yet, unfortunately, this is the basis of persuasion of most climate literature, junk science, and propaganda. There is no equilibrium. There are many mass action equations to be solved simultaneously, i.e., this is not a simple ratio based on volume or mass. The hydrosphere absorption and release of CO₂ happens in a matter of seconds and is predominately temperature dependent.

The difficult challenge in calculating the chemistry is created by the interface between the aqueous CO₂ gas and the multiple carbonate buffering systems, reactants and products in ocean…liquid solute phase partitioning. That equilibrium condition does not exist which makes Henry’s law calculation multidimensional. The reactions are in continuous and chaotic flux. Henry’s law is pulling and pushing the aqueous CO₂ side while dissolution, ionization, sedimentation, resolvation, and weathering are chaotically pulling and pushing the carbonate side. All of the above is perturbed by changes in atmospheric and hydrosphere flows, temperatures, chemical matrix, salinity, pH, and water pressure.

The total atmospheric CO₂ concentration represented by the Mauna Loa, Hawaii Keeling curve shows an almost straight line degree of annual change from 337 ppm in 1979 to 418 ppm in 2021. The rate of change in annual anthropogenic global fossil-fuel carbon emissions is shown to be, in five year time frames, from 1979 to 1999, as follows; 1979-84 -89, 1984-89 +817, 1989-94 +169, 1994-99 +344, 1999-2004 +1,197, 2004-2009 +933. This shows that the Keeling curve reflecting total atmospheric CO₂ concentration is not materially affected by annual anthropogenic global fossil-fuel carbon emissions.

On March 19, 2020, the COVID19 related lockdowns took effect virtually worldwide. From the period of March 20, 2020 to March 20, 2021 there was a rough order 30% reduction in the use of hydrocarbon fuels worldwide across all energy sectors of residential, commercial, industrial and transportation. Yet on March 20, 2021 the Mauna Loa Keeling curve continued its rise to nearly 418 ppm. In other words, even with a massive reduction of worldwide fuel use, the CO₂ trends recorded at Mauna Loa continued to rise in a slope undetectably different from that over the last 50 years.

This suggests that the amount of change introduced by CO₂ from Man’s use of hydrocarbon fuels and cement production is far lower than the “seasonal variations” depicted on the curve by the jagged red “sharks tooth” curve.

This article attempts to explain the myriad of interactions and conclusively show that “the total amount of CO₂ in the atmosphere is independent of biogenic and anthropogenic CO₂ generation and primarily dependent on temperature,” as first stated in the abstract above.

The atmospheric concentration of carbon dioxide gas is continuously adjusting to maintain the concentration partition ratio K derived in Henry’s law. Henry’s law partition ratio is independent of the source of the CO₂. The net average atmospheric concentration of CO₂ (~400 ppmv) is independent of human CO₂ emission. Human CO₂ is fully compensated in (and only a small part of) the natural global CO₂ fluxes in the environment.

Ocean has been estimated to make up 98% of the hydrosphere. (Mason, 1958) Rainwater is less than 2% of the hydrosphere. Mason points out that ocean is 98% of the hydrosphere but he does not specify the rain portion, but he states that no significant error will be made by assuming the average CO₂ concentration in all water is the average of sea water.

According to Henry’s Gas Law, the giant mass of CO₂ gas in ocean water, on the order of 40,000 gigatonnes of carbon (4 X 10¹³ metric tonnes) and temperature regulate the atmospheric CO₂ gas concentration and the CO₂ fluxes in the atmosphere, ocean, biosphere and even in rainwater droplets. The time frame for each of these fluxes is different. Following Henry’s Law, the high solubility of CO₂ gas in liquid water means the atmosphere is scrubbed of CO₂ gas by the enormous volume of liquid water in the ocean, air and soil.

Flow and flux are not the same. Flux is a directional vector of an amount of material flowing per unit time through a unit area. In this case, the unit area is the surface area of water everywhere which is in contact with atmosphere. A CO₂ flux is the amount of CO₂ flowing per second per square meter of water surface. There are enormous, simultaneous and continuous fluxes of carbon dioxide in two directions, into the atmosphere and into water, controlled by temperature and surface area, and both of these directional fluxes are more than 10 times larger than fossil fuel emissions. Now, please watch the very short video below. Pay close attention to the relatively high Henry’s Law solubility constant K for CO₂ and the professor’s short discussion about ammonia being scrubbed by water due to its very high K. Similar to the professor’s example with ammonia, raindrops, ocean and water in soil scrub CO₂ from the atmosphere based on the Henry’s Law K for CO₂ and water.

“The total CO₂ produced by the burning of the annual production of coal and oil is 6.2 X 10¹⁵ g or about 1/300^th of the amount in the atmosphere today. This might suggest that at the present rate of consumption of fossil fuels atmospheric carbon dioxide will be doubled in 300 years. However, in this connection the importance of the hydrosphere as a reservoir of carbon dioxide should be emphasized; its significance has been discussed by Revelle and Suess (1957). Sea water contains 20 g of CO₂/cm2 of the earth’s surface, as against 0.4 g/cm2 in the atmosphere. Oceanic and atmospheric carbon dioxide are interdependent, the former being a function of the partial pressure of CO₂ in the atmosphere. Thus to double the partial pressure of carbon dioxide in the atmosphere would require the addition of much more than is now present therein, because most of that added would be absorbed by the ocean; similarly to decrease the carbon dioxide in the atmosphere by half would require removal of many times the present content. It is apparent that the oceans, by controlling the amount of atmospheric CO₂, play a vital part in maintaining stable condition suitable for organic life on the earth.” (Mason, Page 211-212.)

Note in the above quotation, the 50:1 ratio of grams of CO₂ in sea water to grams of CO₂ in atmosphere. (20 g of CO₂/cm2 in sea water surface versus 0.4 g/cm2 CO₂ in the atmosphere= 50:1 ratio). This partition ratio of CO₂ gas between water and air is governed by Henry’s Gas Law. The absorption of CO₂ gas into the surface of water is fast (sub-second) and driven primarily by water temperature. Colder water absorbs CO₂. Warm water emits CO₂ gas into the air. The distribution of CO₂ gas horizontally and vertically in atmosphere and ocean water is not as fast, but these chaotic processes will not be discussed here.

The dissolution time of aqueous CO₂ gas into its various dissolved carbonate forms is very fast (seconds.) The chemical reaction of carbonate ions with oceanic buffering systems is very fast (seconds.) The calcium buffering system of ocean will be discussed briefly as an example.

Absorption and emission of CO₂ from the surface of water acts locally on every square centimeter of water surface every second. Normalizing temperature and CO₂ concentration by averaging removes information and adds no value to the analysis. The temperature difference above and below about 26 C are the critical variables which define whether carbon dioxide is being absorbed or emitted at a particular location and time. The temperature controls the direction of the flux. The temperature difference and surface area at that temperature control the amount and the velocity of the flow. All of that information is missing when only a global average temperature is used. “The average temperature of the ocean surface water is about 17 °C (62.6 F).” (Temperature of Ocean Water, University of Michigan. August 31, 2001.) The average temperature of ocean surface water is irrelevant to the Henry’s Law equilibrium and to the solubility chemistry of CO₂ in water. The average of very large chaotic fluxes is a meaningless number with no predictive value.

In the graphic below we can easily see where CO₂ is emitting into air and where CO₂ is absorbing into ocean and soil. A global average temperature would tell us nothing. When temperature exceeds 26 C, CO₂ will be emitted from water. When temperature is less than 26 C, CO₂ will be absorbed into water. We can also infer from this graphic that there are enormous fluxes of atmospheric CO₂ gas from the equator to higher latitudes near both poles. In fact there are many cells in the atmosphere and in the ocean each with its own CO₂ flux.

At a few thousand meters altitude above sea level where water vapor and aerosols condense into liquid water droplets, and anywhere condensation occurs, the surface of water droplets will be either absorbing or emitting CO₂ based dominantly on temperature. Henry’s law determines the solubility of CO₂ gas in all water, not only in ocean water. The CO₂ gas concentration in your beverage is changing in real time.

If the top of a can or bottle of a carbonated beverage is removed, or the beer is tapped from the keg into your glass, initially the CO₂ gas concentration in the liquid beverage will immediately decline because the total pressure of the gases above the liquid is significantly less than the total pressure of the mixed gases above the liquid in the closed keg. After that, the aqueous carbon dioxide gas concentration in your beverage will continue to decline until the liquid and air above it reach the Henry’s Law equilibrium partition ratio K, which is based primarily on the temperature of your beverage.

Addition of certain salts or acids to the liquid increases the aqueous CO₂ gas concentration. Carbonated beverages typically contain a small amount of acid, for example phosphoric acid, to increase retention of aqueous CO₂ gas in the liquid. Rain scrubs chemicals such as sodium chloride from the air which become ionic in raindrops and that in turn changes the aqueous CO₂ gas concentration in raindrops.

Henry’s Law only applies to the solubility of gases into liquids when the gas concentrations are low. When they are low, such as rare gas CO₂ at 400 parts per million, then concentration of CO₂ gas in the liquid and in the air above the liquid can be calculated and measured with very high accuracy and precision. Henry’s Law is the basis of the multi-billion dollar per year scientific instrumentation industry of gas chromatography. GC’s are used routinely in almost all industries involving chemistry from perfumes to paint to healthcare to refineries.

Henry’s Law partition only applies to the gas phase in the liquid, for example aqueous CO₂ gas in ocean, and the gas above the liquid, for example CO₂ in the air. Aqueous CO₂ gas reacts in seconds in water by disassociating into several forms of carbonate ions. These carbonate ions then react with ionic forms of other molecules which are also dissolved in ocean water, for example calcium ions. Calcium ions (Ca⁺²) react with a carbonate ions to form calcium carbonate (limestone, dolomite, CaCO3). This calcium carbonate precipitates as a solid and becomes slurry then stone on the sea floor. This disassociation chemistry is not determined by Henry’s Law. Ocean buffering systems such as this calcium chemistry are removing aqueous CO₂ gas from the Henry’s Law equilibrium equation. This calcium buffering chemistry is very important to the concentration of CO₂ in the ocean and atmosphere and is defined by other laws, as will be briefly mentioned.

A rain droplet falls through air containing CO₂ gas. The CO₂ gas partition ratio between the air and the rain droplet is adjusting in real time (no significant lag, no equilibrium) to the temperature differential experienced in the rain droplet as it falls and the CO₂ concentration in the surrounding air. As the rain droplets fall to earth, in tropical and temperate latitudes when the droplet temperature exceeds 26 C, the droplets emit CO₂ gas. In higher temperate and polar latitudes, when droplet temperatures are less than 26 C, the falling drops will be absorbing CO₂ gas from the air as they fall.

Droplets of water nucleate on particles in the atmosphere. The types of particles vary widely based on geography. Salt and other minerals and gases are carried aloft by wind, currents, convection, storms over ocean. Oceans are ~70% of earth’s surface. Over land the chemical composition of raindrops is much more variable; no simple algorithm is possible. Rain droplet formation is discussed in detail in Professor Murry Salby’s text Physics of The Atmospheric and Climate, 2012.

The chemical composition of raindrops varies with the amount of rain falling during a given time period. Rain (and dew) scrub the air of particulates and gases, e.g., hydrocarbon gases. Hydrocarbon, sulfur and nitric gases are higher concentration in urban areas than over ocean, and these gases are found in raindrops in those areas, again obeying Henry’s Law K for each gas. The same is happening for CO₂, methane, argon, and other gases found in air; each gas has its Henry’s Law solubility K for water. You have probably noticed that the air is cleaner after a good rain.

In general, wherever water temperature is below 26 C, that water is absorbing CO₂ gas in real time, no delay, in proportion to the temperature difference above 26 C and in proportion to the area of water surface which is in contact with air at that temperature. Anywhere water temperature is above 26 C it will be emitting CO₂ gas into air. Rain arriving at ocean surface changes the concentration of CO₂ gas in ocean surface, which will then drive re-equilibration based on Henry’s Law partition ratio in that surface water.

Water droplets in clouds, falling from clouds, and condensing in air sum to a relatively high surface area compared to the flat 2 D surface area of the ocean. Approximately 4πr² verses r². Therefore, taken altogether, the additional sink and source due to raindrops would appear to be significant relative to other sinks and sources. But, building an algorithm to calculate the size of this additional rain sink and source would be as uncertain as predicting the weather, primarily due to variances driven by water in all its phases and chaotic conditions.

For example, in Hawaii near the northern boundary between temperate zone and tropical zone, rain and clouds are cooler than ocean surface. Raindrops have a larger ratio of surface area / volume ratio than ocean surface. Cooler raindrops temporarily increase the aqueous CO₂ gas concentration in ocean surface water in Hawaii and all of the tropics. But since ocean water in the tropics is usually warmer than 26 degrees, that additional aqueous CO₂ gas will be rapidly (seconds) emitted to atmosphere as the temperature of the cooler rainwater rapidly warms to the temperature of the ocean’s massive heat sink. Thus, raindrops are another large, chaotic CO₂ gas flux between sink and source. It would be difficult or impossible to model with accuracy this chaotic bi-directional CO₂ flux between sink and source.

To calculate how much CO₂ is in rain, we would need to know the amount of precipitation that is liquid, the surface area of rain drops, the temperature gradients in the global atmosphere and ocean, of course Henry’s Law for myriad conditions, etc. Some of the needed information is measured and estimated. Volume of global precipitation is calculated by taking the product of the Earth’s surface area and its average annual rainfall. Total annual volume of precipitation of water in all phases is about 5.1 × 10¹⁴ m³. In other words, fossil fuel CO₂ gas emission on the order of 5.5 X 10⁹ metric tons (see graphic) is being absorbed into a volume of rain that is on the order of 10¹⁴cubic meters. Raindrops are a large sink and source for CO₂ gas. Rain is scrubbing the air of CO₂ just as it scrubs air of other gases and particles. Whether rain is a sink or source of CO₂ depends on temperature in that location.

The following graphic of the carbon cycle is routinely provided by UN IPCC and other proponents of anthropogenic global warming. Notice that rain is not included. Also the graphic implies that the different CO₂ sources and sinks are not connected. It also implies that fossil fuel emission is only emitted and not absorbed, implying that it remains in the atmosphere. However, in fact, these fluxes into air and into ocean are connected by Henry’s Law and other laws of chemistry and physics.

The Carbon cycle graphic above. The figures indicate carbon storage and flows, expressed in gigatonnes One gigatonne is 1,000 million metric tonnes of carbon or 1 billion metric tonnes. A tonne is a metric unit equal to 1000 kilograms or 10⁶ grams. A gigatonne is 10⁹ grams. One metric tonne equals 1.102 tons. A ton is non-metric old English or American unit sometimes called a short ton. A ton is 2000 pounds. A tonne is about 10% more than a ton. The arrows are proportionate to the volume of carbon. The figures for the flows express amounts exchanged annually. Year: 2009. From collection: Kick the Habit: A UN Guide to Climate Neutrality. Cartographer: GRID-Arendal. www.grida.no/resources/5390

Notice in carbon cycle graphic, CO₂ gas in the ocean surface is about 1020 gigatonnes (1.020 X 10¹² grams), while absorption into ocean surface is about 92 gigatonnes, (9.2 X 10¹⁰ grams) while the estimated fossil fuel CO₂ emission into air is 5.5 gigatonnes (5.5 X 10⁹ grams), but the implication of this graphic is that 5.5 gigatonnes of fossil fuel emission is not mixed with or absorbed by the environment. In fact, fossil fuel CO₂ is immediately and continuously mixed with CO₂ already in the environment, i.e., during a year about 5.5 gigatonnes of fossil fuel CO₂ is mixed with about 92 gigatonnes of atmospheric CO₂ and that mixed CO₂ is also mixed continuously with 1020 gigatonnes of CO₂ in ocean surface. The author/artist and global agencies and governments and AGW proponents clearly imply that CO₂ emission from fossil fuel is a net addition of CO₂ to the atmosphere; this is false. In fact, using numbers from their graphic, there is an immediate dilution of more than 16 times of CO₂ (5.5 divided by 92) which is immediately and continuously diluted again by more than 10 times (5.5 + 92 = 97.5. Then 97.5 divided by 1020). In a ratio of about 50:1, atmospheric CO₂ from all sources is being absorbed into ocean surface where water is cold and about 1 part in 50 is emitted into air where ocean surface water is warm, and both absorption and emission are happening in seconds simultaneously and continuously.

All of these amounts of CO₂ gas shown in the atmosphere are soluble into an annual volume of water precipitation of about 5.1 × 10¹⁴ m³ Unfortunately we do not know the ratio of liquid water precipitation to solid water precipitation remaining as solid ice or snow. This is a rough estimate. A cubic meter equal 1000 liters. Annual water precipitation is about 5.1 X 10¹⁷ liters. Using the annual fossil fuel emission from the graphic above, 5.5 X 10⁹ grams of CO₂ is diluted into 5.1 X 10¹⁷ litersof water precipitation. 5.5 X 10⁹ grams CO₂ divided by 5.1 X 10¹⁷ liters of water equals a concentration of 1.08 X 10^-8 grams of CO₂ per liter of water. One gram per liter equals 1000 parts per million. 1.08 X 10^-8 X10³ = 1.08 X 10^-5 parts per million. In sum, the estimated annual fossil fuel emission of 5.5 gigatonnes of CO₂ is only about 0.000108 ppm in annual water precipitation. It appears that annual rain could easily absorb all annual fossil fuel CO₂ emissions.

According to Henry’s law ratio of 50:1 equals about 2000 ppmv aqueous CO₂ gas in ocean water in relation to about 400 ppmv CO₂ gas in air. Since rain is generally colder than surrounding air and less than 26 C, and rain contains only about 0.000108 ppm of CO₂, this strongly suggests that in general rain will be strongly absorbing CO₂ from air in order to reach a Henry’s equilibrium of 2000 ppmv in water.

On average, rainwater itself has more than enough surface area and raindrops have a large CO₂ concentration deficit. However, rain is notoriously difficult to predict, and absorption and emission are caused by local conditions, not global averages. However, the surface of the ocean is larger and ever present and more than sufficient to scrub all human-produced CO₂ annually, and scrubbing by rain is additional to ocean. As mentioned above, ocean buffering systems are continuously removing aqueous CO₂ gas from ocean water and producing limestone and other carbonate rock and sedimentation. Ocean has “an almost infinite buffering capacity” for CO₂. (Segalstad, page 820. Stumm and Morgan; Segalstad and Jaworowski, 1991).

CO₂ gas concentration in air and ocean is independent of human emission. (Salby). CO₂ concentration in air is observed as the net residual difference between net emission of CO₂ minus net absorption of CO₂, that is about 400 ppmv. (Salby) That net residual difference is determined primarily by temperature changes in ocean and soil, according to Henry’s Law. Driven dominantly by temperature, all CO₂ emissions from all CO₂ sources are compensated by natural adjustment of the partition ratio of CO₂ gas concentration in air versus the aqueous CO₂ gas concentration in the surface of all water. This equilibration is occurring rapidly and continuously worldwide, where locations in northern latitudes will be absorbing CO₂ and latitudes in or near the tropics are emitting CO₂. Human CO₂ emissions (~5.5 gigatonnes per year) into atmosphere are immediately diluted into an order of magnitude (more than 16 times) larger CO₂ sink (~ 90 gigatonnes of CO₂) in the atmosphere. Then, atmosphere in contact with ocean results in another order of magnitude (10 times) dilution into the 1020 gigatonne sink of CO₂ gas in the surface of the ocean. Dilution into ocean surface begins immediately in seconds.

There is another significant dilution. As mentioned above, aqueous CO₂ gas in ocean water (~ 2000 ppmv) is continuously diluted and removed from ocean and from the Henry’s Law equilibrium by rapid dissolution into the multiple vast inorganic ionic buffering systems in ocean water. (Mason. Segalstad. Stumm & Morgan.)

“The upper 200 m of ocean water contains enough dissolved calcium to bind all human produced Anthropogenic CO₂ as precipitated calcium carbonate (in the ocean) without affecting the ocean’s pH (Jaworowski et al., 1992a; Segalstad, 1996; 1998).” (Segalstad, page 818)

This is only the calcium buffering system, one of several oceanic buffering systems. All human CO₂ emission, not only one year’s emission but all human emission, could be dissolved in only the top 200 meters of ocean water by the calcium buffering system alone. (Segalstad) This follows from the relative abundance of the carbonate, calcium and hydroxyl ion reactants in the ocean buffering chemistry reactions.

In seawater, the Ca²⁺ ion is 2.9 times more concentrated than the carbonate (HCO3^–) ion (0.4121 g/kg vs 0.1424 g/kg) (Stumm & Morgan). Dissolution into this calcium buffering system is very fast (seconds.) This is easily demonstrated by blowing bubbles through a straw into a water solution containing calcium hydroxide [Ca(OH)₂ i.e., caustic lime] at its oceanic concentration. Within seconds, the CO₂ in your breath forms a cloud of white calcium carbonate solid in the water and precipitates to the bottom of the container. The requirements for this precipitation are excess calcium ions and excess hydroxyl ions ( OH^– ) ; ocean water surface has both. The hydroxy ion concentration is observed as the alkaline pH of ocean water. The same fast precipitation rate occurs in ocean water. This process continuously removes aqueous CO₂ gas from ocean water, converting it through several intermediate ionic carbonates and then to solid precipitate stone thus continuously driving absorption of more CO₂ gas into ocean water to maintain Henry’s Law partition between ocean and air. The ocean calcium buffering system is a gigantic, continuous CO₂ sink. Limestone and similar carbonate rock are plating on ocean floor in mid-ocean depths controlled by temperature and water pressure at depth. Converting this solid carbonate stone back into atmospheric CO₂ gas requires volcanic temperatures, a chemistry well known for centuries in production of cement by burning limestone which emits CO₂ gas. Some “climate science” literature argues this ocean buffering chemistry operates in time frames of hundreds to thousands of years. That is only half true. The sink (absorption) side of this chemical reaction is ongoing continuously and happens in seconds. Only the source side (emission) of this chemistry, i.e., emissions from volcanic eruption processes, is long term.

“The Law of Mass Action ensures when all these chemical reactions have been accounted for in the total net reaction (and when increasing the amount of a gas, CO₂, in the air), calcium carbonate (solid) will be stabilized in the ocean, because the chemical reaction will be forced in the direction from left to right. This result is the opposite of what is commonly asserted (that solid calcium carbonate would be dissolved by the increasing amount of CO₂ in the air).” (Segalstad, page 819)

“The loss of carbon dioxide from the atmosphere by deposition as carbonate and organic carbon in sedimentary rock was estimated by Rubey as totaling 920 X 10²⁰ g. More recently, Wickman (1956) has published some revised figures. He places the amount of carbonate carbon per square meter of earth’s surface as 2420 +/- 560 g and of organic carbon at 700 +/- 200 g. Taking the figure of 3100 g/m=cm2 for the total amount of carbon transferred from the atmosphere to the sedimentary rock, this is equal to a total of 158 X 10²⁰ g of carbon, or 580 X 10²⁰ g of CO₂. This latter figure is of the same order of magnitude as Rubey’s but considerably lower. The figures show clearly that the amount of carbon dioxide deposited in sedimentary rocks far exceeds the amount in the present atmosphere, hydrosphere, and biosphere (about 1.5 X 10²⁰ ), and thus indicate that large amounts of carbon dioxide must have been released from magmatic sources throughout geological time to maintain organic activity. Wickman’s figures show, in addition, that far more carbon dioxide has been removed as limestone and dolomite than as coal or other organic carbon.” (Mason, page 209)

All of the above CO₂ sinks and sources turn over in months except the emission of CO₂ from limestone and other carbonate rock. This monthly rate is inferred from NOAA Mauna Loa CO₂ data. The large (two to four times) differences in the annual rates of change of slope (i.e., accelerations) which are observed are stated to be due to seasonal photosynthesis and ice cover differences between the northern and southern hemispheres. The zig-zag “sharks teeth” within-year changes in slope are about +3.5 to -7 to +3.5. These are the annual seasonal “sharks teeth” on the NOAA Mauna Loa CO₂ slope (graphic below.) These rapid within year accelerations are compared to an average slope (1.5 ppmv per year to 2 ppmv per year depending on year) of the net global atmospheric CO₂ concentration. A very, very large rate-compensated drain is inferred from within-year difference observed in the 400 ppmv residual of two gigatonne fluxes (CO₂ emission and CO₂ absorption). CO₂ absorption accelerates then sharply decelerates then sharply accelerates again. These small changes in sign and acceleration are residual differences between two enormous (gigatonne) CO₂ fluxes in opposite directions. The analogy is the temperature and area of the surface of water act as a temperature controlled adjustable-rate CO₂ valve controlling the fluxes between ocean and air. Add more CO₂ from any source and the system adjusts the rate in both time and volume to achieve Henry’s K partition… without regard to the source of the CO₂. And vice versa.

Henry’s law partition is independent of the source of the CO₂. The net average atmospheric concentration of CO₂ (~400 ppmv) is independent of human CO₂ emission. For example, during the 2020 corona virus pandemic, fossil fuel CO₂ emission is estimated to have decreased by 20% to 30%. At the same time, net global average CO₂ trend increased by about 2 ppmv for 2020, rather than decreasing, as observed by the NOAA lab on Mauna Loa and shown in the graphic above; this demonstrates that the net global average atmospheric concentration of CO₂ is independent of human CO₂ emission. The CO₂ trend is a function primarily of temperature. This relationship is explained in detail including derivation of the equations in the video lecture at the link in the references below (Salby), Murry Salby, Professor of Atmospheric Physics and author of two texts on the subject.

On a time scale of millions of years, atmospheric CO₂ has been in a steady declining trend. Ocean is absorbing CO₂ from air, the aqueous CO₂ gas ionizes, then reacts to produce limestone and other sediment and rock on the walls and floor of the ocean.

Any and all additional CO₂ added to the air from any and all sources will enter the ocean surface and be balanced in an Henry’s Law equilibrium of approximately 50:1 ratio between water and air at the specific temperature in that location.

The graphic of net global average CO₂ concentration, for example from the NOAA Keeling Laboratory on Mauna Loa in Hawaii above, is a graph of an equilibrium equation. The equation for the line on the graph is controlled by temperature. Temperature controls the ratio of the CO₂ in the air versus the aqueous CO₂ gas in water. The line on the graph is recording the points where the net global flux of CO₂ into the air is in equilibrium with the net global flux into water in all its liquid forms at a specific temperature. If temperature is increasing, then relatively more CO₂ is emitted from water into air. If temperature is decreasing, then more CO₂ is absorbed into water.

An equilibrium equation which is a function of temperature is explained in this short video. Simply substitute CO₂ where the professor has H2O as his example. In the case of CO₂, temperature is driving the Henry’s Law equation for the ratio of CO₂ gas in water versus CO₂ gas in air.

The multiyear long term trend (or slope) in net global average CO₂ concentration (NOAA Mauna Loa graphic above) is the result of slowly increasing surface temperature since the end of the last ice age.

Ocean surface is about 70% of the surface of the earth. The ocean is the lung of all life on earth, breathing out life-giving CO₂, and breathing in life-giving CO₂.

Carbon is the fundamental building block of life on earth, a major component molecule for every cell in all life forms on earth with exception of a few very rare bacteria in deep ocean volcanic vents and these rare bacteria still contain carbon. All of the carbon in all of your cells was at one time CO₂ in the air. All of the carbon in every cell of every plant, animal, insect, fish, etc. was once CO₂ gas in the air. The ONLY way that carbon gets into living things is by plants absorbing CO₂ from the air for photosynthesis and then other living things eat those plants.

People and plans to reduce atmospheric CO₂ are functionally a eugenics death cult which would, if successful, reduce sustainability of life on earth by resulting in less food and ultimately lower population of all living things. For example, plans by billionaires, governments and quasi governments to create artificial clouds to block the sun would intentionally cool ocean surface. As you now know from the discussion above, this would remove CO₂ plant food from air and starve plants, crushing food supply for all life. Such plans to cool the planet could force rapid absorption of CO₂ into ocean in amounts far in excess of the amount of CO₂ produced by humans. If humans cool the surface and force the carbonate chemistry to the right, to more products and more stone, then life may never recover. It may be possible to geoengineer clouds to cool the oceans and force absorption of CO₂. But when they discover the mistake, warming will be much more difficult or impossible. These are very dangerous geoengineering plans driven by ideology not science or common sense and if done or seriously attempted most likely humanity will have sealed its fate in stone.

During the authors’ lifetimes, all of humanity has been buried by a non-stop, extremely well-funded propaganda campaign designed to convince people to feel guilty about their carbon footprint and to fear a never-ending list of climate catastrophes, all caused, so they claim or imply, by human-produced CO₂. Their propaganda and funding has been accelerating since the 1960s following the required reading of “The Population Bomb” and “Ecoscience.” This mistaken ideology is based on the 18th century mistaken calculations of Thomas Malthus who believed that human population growth would exhaust earth’s natural resources. Although Malthus’ forecasts have never happened, including the fact that human population growth rate has been declining for decades, his ideology has been adopted by the wealthy, the influential, the UN and over 100 governments, academics and major corporations. Wittingly or not, they are driving what is in fact a globally destructive eugenics campaign financed by trillions of dollars. The pace and intensity of the propaganda campaign will accelerate as the date approaches for the next UN IPCC climate conference, as it always has. This is a dangerous, gigantic global fraud. “Stop treating it [i.e. AGW…human-caused global warming/climate change] as a worthy opponent. Do not ascribe reasonableness to the other side. It is not reasonable, not true, not even plausible.” ~ Richard Lindzen, Professor Emeritus, Alfred P. Sloan Professor of Meteorology, Massachusetts Institute of Technology. (31 March 2021. Zoom call Clintel Foundation)

Conclusion

As we have demonstrated, the relationship in carbon dioxide content between the Earth’s biosphere and atmosphere is predominately controlled by Henry’s law. The ratio is approximately 50:1and the controlling factors are the turbulent and chaotic atmospheric flows and the spatial surface temperature gradients of the world’s oceans.

The real time relative percentage of anthropogenic CO₂ in the total atmospheric quantity of CO ₂ falls below the signal to noise ratio of current measurement procedures.

The often recited concept of CO₂ atmospheric residence time has been proven indeterminate and meaningless.

The theoretical hypotheses of anthropogenic carbon dioxide induced global warming cannot be assumed a priori; AGW/climate change is therefore falsified.

Authors Next Steps

The authors have asserted that the spectrometry or measurement equipment used today to measure global carbon dioxide levels and the techniques used to interpret such measurements and convert them to real numbers is not capable of resolving the anthropogenic portion of CO₂ due to “signal to noise ratio” issues.

The authors have teamed together with a team of Stanford University Ph.D. physicists and mathematicians to produced advanced physical and mathematical techniques to improve the signal to noise ratio and accurately measure the anthropogenic CO₂ content of the atmosphere.

In efforts of full disclosure to the scientific community and public alike they have filed for a patent as follows:

A Preferred Means to Calculate Ratio of Anthropogenic Carbon Dioxide Produced by Human Combustion of Fossil Fuels Relative to Earth’s Measured Carbon Dioxide Atmospheric Reservoir

Abstract

It is estimated that the worldwide annual costs associated with global warming and related alternative energy exceeds 2 trillion U.S. dollars. Countries worldwide are now taking actions or considering actions costing hundreds of billions, even trillions of dollars. However, Anthropogenic Global Warming (AGW) or human caused climate change has not been proven. Therefore the ability to falsify the anthropogenic theory of climate change has enormous financial and societal benefits with significant return on investment. Whereas studies involving the absorption of infrared light reflected from the Earth’s surface and then retransmitted to the Earth by so called greenhouse gases have been ongoing for many years, this scientific discipline has been unable to prove or disprove the degree to which anthropogenic processes are responsible for any AGW or climate change on the Earth. Since the primary mechanism of the speculated climate change is predicated on burning of fossil fuel sources by man which produces carbon dioxide gas, then a definitive means of determining the influence of man’s contribution, if any, to AGW or climate change is to accurately determine what percentage of the total amount of carbon dioxide resident in the Earth’s lower atmosphere results from burning fossil fuels worldwide. Given the dynamic structure of the Earth’s “carbon system” involving the natural variabilities in carbon dioxide emission and absorption, the ability to mathematically derive the percentage of measured anthropogenic fossil fuel CO₂ which is contributed to the Earth’s total reservoir of atmospheric carbon dioxide gas has been virtually impossible due to factors involving the variations within the carbon dioxide flux. The object of the proposed invention and method of calculation solves these issues and provides an accurate means to empirically demonstrate and define the anthropogenic carbon dioxide contribution due to humans burning fossil fuels. To the extent that such a contribution is proven to be extremely small, anthropogenic global warming and climate change becomes falsified and continuing mitigation expenses become unwarranted.

A feasibility study is currently in process and the results are expected by the end of July, 2021. Final results of the project along with definitive verifiable numbers are expected by Q2, 2022.

The authors fully expect the results of this project to be “earthshaking.” This effectively falsifies AGW/climate change once and for all and deflates if not defeats the $2.5 trillion dollar worldwide annual green energy and climate mitigation boondoggle. It is anticipated that defense councils in most if not all of the frivolous lawsuits brought against oil and energy companies will seek licenses to the patent, its results and access to our team as expert witnesses, as they seek dismissal of these suits.

References:

(Salby) Lecture by Professor Murry Salby, PhD. https://youtu.be/b1cGqL9y548

(Mason) Mason, Brian. Principles of Geochemistry. 2^rd Edition. 1958. https://archive.org/details/principlesofgeoc0000unse/page/212/mode/2up

(Segalstad) Segalstad, Tom. Some thoughts on ocean chemistry (Chapter 6.3.1.2). January, 2014. In book: Climate Change Reconsidered II – Biological Impacts. Page 818, 819. https://www.researchgate.net/publication/304797201_Some_thoughts_on_ocean_chemistry_Chapter_6312

Carbon cycle graphics: https://grid-arendal.maps.arcgis.com/apps/MapJournal/index.html?appid=a49488a79f6644c290f7e01a29f57fc7

(Stumm & Morgan) Stumm, Werner; Morgan, James J. aut. Aquatic chemistry : an introd. emphasizing chemical equilibria in natural waters. 1981. https://archive.org/details/aquaticchemistry00stum/page/566/mode/2up

Segalstad, T.V. and Jaworowski, Z. 1991. CO₂ og globalt klima. Kjemi51: 13–15.

“Annual average global precipitation is approximately 1123 mm (gauge corrections considered), which is consistent with other reported values. (Chonka-PTT)” = 5.73 × 10¹⁴ m³ (Legates, David R., Cort J. Willmott. Mean seasonal and spatial variability in gauge-corrected, global precipitation. International Journal of Climatology 10(1990): 111-127.)

About the Authors

Bud Bromley:

Bud’s entrepreneurial leadership exceeded three decades. He was the senior business development, marketing and sales executive at four public corporations, each company a supplier of analytical and life sciences instrumentation, software, consumables and service. Prior to those positions, his 19 year career in Hewlett-Packard Company’s Analytical Products Group included worldwide sales and marketing responsibility for Bioscience Products, Global Accounts and the International Olympic Committee, as well as international management assignments in Japan and Latin America. Bud has visited and worked in more than 65 countries and lived and worked in 3 countries.

Tomer (Tom) Tamarkin:

In 1971 Tom received the nation’s highest honor for high school students in the field of physics for his work in nuclear magnetic resonance. He did his undergraduate studies in physics, with a dual minor in math and chemistry, at N A U in the 1971-75 timeframe. He has been in the energy generation and utility industry since 1985. Tom was the inventor of electric utility energy conservation instrumentation and measurement devices. He has been granted seven patents in the U.S., Israel, Europe, & China. In the U.S. alone his patents are practiced by the nation’s largest utility companies on over 90 million installed devices.

Tom spends roughly ½ of his “working time” lecturing, writing articles, and working with prominent Ph.D. level scientists on what he calls the greatest deception and fraud ever created by man against mankind; AGW climate change.

In 2019 Tom formed ClimateCite, Corp., a U.S. IRS 501(c)(3) compliant not for profit company to further his efforts in defeating the climate hoax worldwide.

Tom married his wife, Emily J. Tamarkin in 1982 and the two of them live together in Carmichael, California. They have one son, Jeremy A. Tamarkin.