by Bud Bromley
Image: Union of Concerned Scientists
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.
Ocean has been estimated to make up 98% of the hydrosphere. (Mason, 1958)
Rainwater is less than 2% of the hydrosphere.
According to Henry's Gas Law, the giant mass of CO2 gas in ocean water, on the order of 40,000 gigatons of carbon (4 x 1013 metric tons) and temperature regulate the atmospheric CO2 gas concentration and the CO2 fluxes in the atmosphere, ocean, biosphere and even in rainwater droplets.
The timeframe 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.
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.
enormous, continuous fluxes of CO2 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.
Similar to the professor's example with ammonia,
Note in the above quotation, the 50:1 ratio of grams of CO2 in sea water to grams of CO2 in atmosphere.
The partition ratio of CO2 gas between water and air is governed by Henry's Gas Law which results in about 50 times higher concentration of CO2 gas in water than in the air around or above the water.
The absorption of CO2 gas into the surface of water is very fast (sub-second) and driven primarily by water temperature.
The distribution of
CO2 gas horizontally and vertically in atmosphere is not as fast,
but I will not discuss these chaotic processes here.
The calcium buffering system of ocean will be discussed
briefly as an example.
The temperature difference above and below about 26ºC are the critical variables which define whether CO2 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 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.
When temperature is less than 26ºC, 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.
Henry's law determines the solubility of CO2 gas in all water, not only in ocean water.
Addition of 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, for 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.
all I will say about this subject here...
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.
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, sedimentation, 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, but I will only briefly mention it in this article.
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 and the CO2 concentration in the surrounding air as the droplet falls.
As the rain droplets fall to earth, in tropical and temperate latitudes when the droplet temperature exceeds 26ºC, the droplets begin emitting CO2 gas.
In higher temperate and polar latitudes, when
droplet temperatures are less than 26ºC, the falling drops will be
absorbing CO2 gas from the air as they fall.
Oceans are ~70% of earth's surface. Over land the chemical composition of raindrops is much more variable; no simple algorithm is possible.
formation is discussed in detail in Professor Murry Salby's text
Physics of the Atmosphec and Climate, 2012.
The same is happening for CO2, methane, argon, and other gases found in air:
You have probably noticed that
the air is cleaner after a good rain.
Anywhere water temperature is above 26ºC 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.
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.
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.
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 below graphic) is being absorbed into a volume of rain that is on the order of 1014 cubic 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.
Also the graphics imply that the different CO2 sources and sinks are not connected. They also clearly imply that fossil fuel emissions are only emitted and not absorbed.
However, in fact, all of these fluxes into air and into ocean are
The implication of this graphic is that 8 gigatons of fossil fuel emission is not mixed with or absorbed by the environment.
The author/artist and global agencies and governments and AGW proponents clearly imply that CO2 emission from fossil fuel is a net addition of the CO2 to the atmosphere:
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! that is annual rainfall.
That net residual difference results primarily from temperature changes in ocean and soil, following 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 aqueous CO2 gas concentration in surface water.
This equilibration is occurring rapidly and continuously.
There is another significant dilution.
As mentioned above, aqueous CO2 gas in ocean water is continuously diluted and removed from ocean and from the Henry's Law equilibrium by rapid dissolution into carbonates joining the multiple, vast inorganic ionic buffering systems in ocean water. (Mason)(Segalstad.)
Note this is only the calcium buffering system, one of several oceanic buffering systems.
The average abundance,
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 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 surface has both, which is measured by the alkaline pH of ocean water indicating excess hydroxyl ions.
The same fast precipitation rate occurs in ocean water.
This process continuously removes aqueous CO2 gas from the water, converting it to ionic carbonates and then to solid precipitate stone thus driving continuous 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 rock is plating on ocean floor in mid-ocean depths controlled by temperature and water pressure.
Converting this solid calcium carbonate (limestone) back into atmospheric CO2 gas requires volcanic temperatures, a chemistry well known for centuries by production of cement by burning limestone.
Some "climate science" literature argues this ocean buffering chemistry operates in time frames of hundreds to thousands of years.
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., CO2 emissions from a volcanic eruption is long term.
This monthly rate is inferred from NOAA Mauna Loa data.
The large (two to four times) differences observed in the within-year rates of change of slope are stated to be due to seasonal photosynthesis and ice cover differences between the northern and southern hemispheres.
Within-year changes in slope are +1.5 to +3.5 to -7 to +3.5 and more and returning to the +1.5 ppmv per year annual slope.
These are the annual seasonal "sharks teeth" on the NOAA Mauna Loa CO2 slope (graphic below.).
These rapid within-year changes in slope are
compared to the ongoing annual rate of change of slope (1.5 ppmv per
year) of the net global atmospheric CO2 concentration.
A small change in net CO2 concentration on the NOAA Mauna Loa slope represents the residual difference between two enormous (gigaton) CO2 fluxes in opposite directions.
The temperature and area of the surface of water act as an adjustable-rate CO2 valve 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...
This is explained in detail including derivation of the equations in the video lecture at the link in the references below, by Dr. Murry Salby, Professor of Atmospheric Physics and author of two graduate school level textbooks on the subject.
As mentioned above, the oceanic buffering systems are continuously removing aqueous CO2 gas from ocean water and producing limestone sedimentation.
On a time scale of millions of years, atmospheric CO2 has been in a steady declining trend.
have been fewer volcanic eruptions and open fissures at volcanic
temperatures which would reverse the chemical reaction equation and
convert the limestone rock back into CO2.
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.
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.
Contrary to the claims by proponents of human-caused global warming, human-produced CO2 does not stay in the atmosphere.
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.
Carbon is the fundamental building block molecule for every cell in all life forms on earth.
All of the carbon in all of your cells was at one time CO2 in the air. Carbon is a major component of all cells.
All of the carbon in every cell of every plant, animal,
insect, fish, bacterium, virus, etc was once CO2 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.
For example, plans by billionaires and governments to create artificial clouds to block the sun would intentionally cool ocean surface and as explained above.
As you now know from the discussion above, this catastrophic plan would remove CO2 plant food from air and starve plants, crushing food supply for all life:
During my seventy plus year lifetime, 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, they claim or imply,
This mistaken ideology is based on the 18th century mistaken calculations of Thomas Malthus who believed that,
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 corporations.
They are driving what is in fact a globally destructive eugenics campaign financed by trillions of dollars.
This is a dangerous, gigantic global fraud.