I believe the article at the link below dovetails nicely the Henry’s Law theory (second link below).
Since humidity has been decreasing (according to data therein) then insolation of ocean surface has been increasing, then the area of ocean surface which is above 25.6 C has been increasing, then CO2 emissions from ocean surface has been increasing, therefore the slow average ~2.5 ppm per year slope in Mauna Loa measured net global atmospheric CO2 concentration.
Bud is a retired life sciences executive. 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 based in Japan and Latin America. Bud has visited and worked in more than 65 countries and lived and worked in 3 countries.
Bud Bromley, thanks for the feedback.
Cause of relative humidity drop- 81% of the relative humidity decrease is generated by a CO2 induced 0.70%/year plant water use efficiency increase. See my paper, page 21, Botanical Quantifications, calculation on page 22.
Concerning Henry’s law application to ocean and atmospheric CO2 concentration- Henry’s law unfortunately does not apply because the liquid and gas must be in equilibrium contact, not the case. “Henry’s law is a gas law that states that the amount of dissolved gas in a liquid is proportional to its partial pressure above the liquid. The proportionality factor is called Henry’s law constant. H = Ca / p.” The ocean on average is ~5% saturated (undersaturated) with CO2 per Henry’s law at 410ppm CO2 in atmosphere and 41ppm average CO2 in oceans.
See my paper, calculation on page 6, Problem 4. The ocean concentration is limited by mass transfer between liquid ocean and gas atmosphere, not by CO2 solubility in sea water.
I hope this helps. My email is davidmotes7-at-gmail-dot-com if you want to contact me. Thanks! David.
David, you don’t quite understand Henry’s Law, which most certainly does apply. I can help if you want. This is all observable by lab experiments by gas chromatography with a temperature controlled headspace accessory. This was once taught in analytical chemistry wherein the student confirmed the chromatographic calibration curves by stoichiometric titrations. Henry’s is a phase-state equilibrium equation. Unfortunately for climatology, this equation is usually mistakenly merged for simplicity as a hypothetical value with one or more acid-bases equations of CO2 hydration reaction or subsequent carbonate ion reactions. This leads to significant errors, larger than the variations in concentration due to human emissions.
The Henry’s phase-state equation is usually NOT in equilibrium, but instead is usually changing to restore the equilibrium partition ratio for a specific temperature at a area of ocean surface which is out of equilibrium. The Henry’s “constant” and partition ratio vary primarily by ocean surface temperature, which already should explain what I wrote above. The ratio is not constant with respect to ocean surface temperature, which means the CO2 concentration of aqueous CO2 gas in ocean surface and the concentration of CO2 gas above that surface changes with temperature changes in ocean surface temperature, and ocean surface temperature changes primarily (but not only) due to insolation. Henry’s Law rearranges as d(ln(kH))/d(1/T) to define the temperature dependence parameter in Henry’s Law partition co-efficient, where kH is the Henry’s Law constant and T is temperature in Kelvin. The solubility of CO2 gas in ocean surface depends primarily on the temperature of the ocean surface, that is at the interface of the gas and liquid. Changes in ocean surface temperature change the activity of the molecules in the ocean surface. When the Gibbs free energy and virial activities are exceeded, the aqueous CO2 gas molecules at the surface break surface tension and are emitted into air. Mass transfer at the surface is NOT a rate limiting step, but rather occurs in sub-second time if the CO2 is present in the air or surface.
When surface is above about 25.6 C, the CO2 flux into air depends on the surface area at a given temperature. The rate limiting step to return to the partition ratio for a given ocean surface temperature is the migration rate of aqueous CO2 gas within the ocean water matrix. Secondarily, there are two thin layers (one at ocean surface, one in the air above the surface) which also can affect the rate of return to the equilibrium ratio. Alkalinity, salinity, and partial pressure of CO2 in air and ocean surface affect the ratio also in local conditions, but averaging across the global surface these secondary variables cancel out leaving temperature of the ocean surface as the controlling variable. For example, if the ocean surface is perturbed by waves, or a ship or buoy sampling ocean water, that increases activity of the molecules in ocean surface, which in turn increases CO2 emissions, de-saturates ocean surface with respect to the Henry’s ratio, and distorts CO2 measurement from the expected Henry’s ratio for that temperature. Or, another example, if surface winds continue for hours, CO2 partial pressure above the surface is reduced, which in turn reduces partial pressure of aqueous CO2 gas in ocean surface, basically depleting the ocean surface of CO2. Thus, there is a time lag for the aqueous CO2 gas to be re-saturated to the Henry’s ratio for that temperature in ocean surface due to the CO2 migration rate in the ocean water matrix. There are many other such examples of continuously changing Henry’s ratio and CO2 concentrations in ocean surface and air above the surface.
In the last decades since satellite measurements began, the area of ocean surface which is above 25.6 C has been increasing. One result of that is CO2 emissions from ocean surface have been slowly increasing. In NOAA and NASA records, changes in air temperature are recorded to always follow SST, and changes in average surface atmospheric CO2 concentration always follow SST. I have these graphs if you want them. The source of the CO2 is not a variable in the Henry’s law phase-state equilibrium equation. If humidity is reducing insolation of ocean surface, then ocean surface temperature will decrease. When or if and where ocean surface area is below about 25.6 C, then ocean surface will be absorbing CO2 from the atmosphere.
Analysis of Temporal Signals of Climate. Peter Stallinga, Igor Khmelinskii. FCT and CEOT, University of the Algarve, Faro, Portugal. DOI: 10.4236/ns.2018.1010037
My email is bud.bromley@outlook.com in case you have questions.
Bud Bromley, thanks for the feedback.
Cause of relative humidity drop- 81% of the relative humidity decrease is generated by a CO2 induced 0.70%/year plant water use efficiency increase. See my paper, page 21, Botanical Quantifications, calculation on page 22.
Concerning Henry’s law application to ocean and atmospheric CO2 concentration- Henry’s law unfortunately does not apply because the liquid and gas must be in equilibrium contact, not the case. “Henry’s law is a gas law that states that the amount of dissolved gas in a liquid is proportional to its partial pressure above the liquid. The proportionality factor is called Henry’s law constant. H = Ca / p.” The ocean on average is ~5% saturated (undersaturated) with CO2 per Henry’s law at 410ppm CO2 in atmosphere and 41ppm average CO2 in oceans.
See my paper, calculation on page 6, Problem 4. The ocean concentration is limited by mass transfer between liquid ocean and gas atmosphere, not by CO2 solubility in sea water.
I hope this helps. My email is davidmotes7-at-gmail-dot-com if you want to contact me. Thanks! David.
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David, you don’t quite understand Henry’s Law, which most certainly does apply. I can help if you want. This is all observable by lab experiments by gas chromatography with a temperature controlled headspace accessory. This was once taught in analytical chemistry wherein the student confirmed the chromatographic calibration curves by stoichiometric titrations. Henry’s is a phase-state equilibrium equation. Unfortunately for climatology, this equation is usually mistakenly merged for simplicity as a hypothetical value with one or more acid-bases equations of CO2 hydration reaction or subsequent carbonate ion reactions. This leads to significant errors, larger than the variations in concentration due to human emissions.
The Henry’s phase-state equation is usually NOT in equilibrium, but instead is usually changing to restore the equilibrium partition ratio for a specific temperature at a area of ocean surface which is out of equilibrium. The Henry’s “constant” and partition ratio vary primarily by ocean surface temperature, which already should explain what I wrote above. The ratio is not constant with respect to ocean surface temperature, which means the CO2 concentration of aqueous CO2 gas in ocean surface and the concentration of CO2 gas above that surface changes with temperature changes in ocean surface temperature, and ocean surface temperature changes primarily (but not only) due to insolation. Henry’s Law rearranges as d(ln(kH))/d(1/T) to define the temperature dependence parameter in Henry’s Law partition co-efficient, where kH is the Henry’s Law constant and T is temperature in Kelvin. The solubility of CO2 gas in ocean surface depends primarily on the temperature of the ocean surface, that is at the interface of the gas and liquid. Changes in ocean surface temperature change the activity of the molecules in the ocean surface. When the Gibbs free energy and virial activities are exceeded, the aqueous CO2 gas molecules at the surface break surface tension and are emitted into air. Mass transfer at the surface is NOT a rate limiting step, but rather occurs in sub-second time if the CO2 is present in the air or surface.
When surface is above about 25.6 C, the CO2 flux into air depends on the surface area at a given temperature. The rate limiting step to return to the partition ratio for a given ocean surface temperature is the migration rate of aqueous CO2 gas within the ocean water matrix. Secondarily, there are two thin layers (one at ocean surface, one in the air above the surface) which also can affect the rate of return to the equilibrium ratio. Alkalinity, salinity, and partial pressure of CO2 in air and ocean surface affect the ratio also in local conditions, but averaging across the global surface these secondary variables cancel out leaving temperature of the ocean surface as the controlling variable. For example, if the ocean surface is perturbed by waves, or a ship or buoy sampling ocean water, that increases activity of the molecules in ocean surface, which in turn increases CO2 emissions, de-saturates ocean surface with respect to the Henry’s ratio, and distorts CO2 measurement from the expected Henry’s ratio for that temperature. Or, another example, if surface winds continue for hours, CO2 partial pressure above the surface is reduced, which in turn reduces partial pressure of aqueous CO2 gas in ocean surface, basically depleting the ocean surface of CO2. Thus, there is a time lag for the aqueous CO2 gas to be re-saturated to the Henry’s ratio for that temperature in ocean surface due to the CO2 migration rate in the ocean water matrix. There are many other such examples of continuously changing Henry’s ratio and CO2 concentrations in ocean surface and air above the surface.
In the last decades since satellite measurements began, the area of ocean surface which is above 25.6 C has been increasing. One result of that is CO2 emissions from ocean surface have been slowly increasing. In NOAA and NASA records, changes in air temperature are recorded to always follow SST, and changes in average surface atmospheric CO2 concentration always follow SST. I have these graphs if you want them. The source of the CO2 is not a variable in the Henry’s law phase-state equilibrium equation. If humidity is reducing insolation of ocean surface, then ocean surface temperature will decrease. When or if and where ocean surface area is below about 25.6 C, then ocean surface will be absorbing CO2 from the atmosphere.
I explain this science in more detail with reference in this blog post: https://budbromley.blog/2021/08/18/henrys-law-controls-co2-concentration-not-humans/ Please read the following references in that post.
Stallinga, P. (2020) Comprehensive Analytical Study of the Greenhouse Effect of the Atmosphere. Atmospheric and Climate Sciences, 10, 40-80. Full paper in pdf here: https://www.scirp.org/pdf/acs_2020011611163731.pdf
Analysis of Temporal Signals of Climate. Peter Stallinga, Igor Khmelinskii. FCT and CEOT, University of the Algarve, Faro, Portugal. DOI: 10.4236/ns.2018.1010037
My email is bud.bromley@outlook.com in case you have questions.
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