GREENHOUSE GASES & THE CO2 DEBATE


The discussion and analysis here should be readily understood by most readers, but some of the theory and interpretation behind the discussion might require some understanding of more advanced level chemistry.  This particularly relates to how greenhouse gases absorb heat from outgoing radiation.  This is most simply explained in the following chart. 

The important point to note is that as atmospheric CO2 increases, the additional absorbed heat that is retained rapidly decreases, getting to the point that even a doubling  (from 400 ppm to 800 ppm in the first graph below) with have  minimal heating impact. Additional atmospheric CO2 at present levels of around 400 ppm will have minimal temperature or climate impact and should not be a concern. At these present CO2 levels, even substantial CO2 mitigation at enormous cost will have minimal cooling impact & not worth even contemplating.  These very important facts are little known in the wider community and the fear and panic being generated is completely unfounded. 


The detail chemistry behind CO2 absorption spectra is particularly well explained in the video clip by Emeritus Professor William Happer,  (Physics Dept, Princeton University) in particular explaining  the nonlinear (logarithmic) nature of the influence of CO2 concentration on the infra red absorption spectra, in the segment from around 23 - 29 minutes:  

 
https://www.youtube.com/watch?v=CA1zUW4uOSw 

Web link: https://www.youtube.com/watch?v=CA1zUW4uOSw

A web link to  a 25 minute YouTube video clip, which is one of the best wide-ranging explanations of the role of CO2 in the atmosphere and climate I have seen is presented by Professor William Harper:


Conversations that matter  with Professor William Happer (25 minutes).  2015 .

Web link:
https://www.youtube.com/watch?v=pHCCE-sw_Sc 

CO2 -    the greenhouse gas of major concern


The stable forms of carbon at the Earth’s surface are: carbon dioxide CO2, bicarbonate ions in solution HCO3-, carbonates (calcite, limestone etc). These three are the most oxidised and therefor the most stable forms of carbon at the Earth's well-oxygenated surface. Other forms of unstable carbon are more reduced and include methane (CH4), carbon monoxide (CO), elemental carbon it self, and living matter. All of these will ultimately oxidise to one of the more oxidised variants in the presence of an oxygenated atmosphere.   

CO2 is the most oxidised form of carbon, forming a stable relatively inert gas in the atmosphere (currently just over 400 ppm). Bicarbonate (HCO3-), is the stable form dissolved in water, which contains 60 times more abundant CO2 than does the atmosphere.  Carbonates are the stable solid form, mainly as calcite (CaCO3 or limestone) and dolomite (CaMg(CO3)2 another form of limestone). Limestones are 44% CO2 by weight and form a major rock type, often entire mountain ranges. More than 99% of all the CO2 component formerly in the Earth’s early atmosphere is now locked up in carbonate rock.   

Atmospheric CO2

Certain trace gases in the atmosphere are thought to maintain the Earth’s temperature at a fairly constant level. These gases are called greenhouse gases & have the effect of preventing incoming visible radiation escaping as infrared radiation. The trapped radiation wave lengths heat up the atmosphere at the surface, but only to a limited extent, dropping off dramatically as their abundance increases (see later comments).

The mean global temperature of the Earth is a warm 15 degrees C . Without these greenhouse gases, all infrared radiation would be lost to space and the global Earth temperature would be considerably lower overall with hot days and very cold nights. Without the atmosphere the Earth’s mean surface temperature would be -18 degrees, rather than the present average of 15 degrees. Variations in greenhouse gases are thought to influence climate, & in the present climate debate CO2 is the greenhouse gas of principal concern.

The main greenhouse gases, their abundance, their thermal influences & the contribution by man are presented in the following table.

Ranking of greenhouse gases vs CO2 in terms of global heat generation capacity:

GREEN HOUSE GAS                                    Heat retention potential (multiple)
Carbon Dioxide (CO2)                                 1
Chloroflourocarbons (CFC’s)                     1,300 TO 9,300
Methane (CH4)                                             21
Nitrous oxide    (N2O)                                 310

Water vapour (this does not include water droplets as in clouds) is a powerful greenhouse gas comprising about 95% of the greenhouse gas inventory & is by far the dominant influence, but does not contribute to what is called the enhanced greenhouse effect because it is not increasing in abundance.
A runnaway greenshouse effect is said to occur when increasing greenshouse temperatures are enhanced by positive feedbacks in the environment that also generate more greenhouse components or other forms of atmospheric temperature increase, (eg increasing water vapour) thus accelerating and exacerbating the climatic effect. Positive feedbacks are generally more than compensated by buffering effects which act to minimise any change in systems at equilibrium.

Pre industrial revolution levels  1750-1800                        1990 levels

              CO2                       280   ppm                                           353 ppm
              Methane                 0.8 ppm                                          1.72 ppm

CO2 dissolved in the ocean is some 60 times that in the atmosphere with more than 85% as bicarbonate ions (HCO3-).

Human activity (fossil fuels & burning biomass), has caused much of the increase. Volcanic gases also produce large amounts of CO2. Burning all the fossil fuels in existence would produce an atmospheric CO2 level of around 2000 ppm. To halve the present levels would probably annihilate all terrestrial vegetation & animal life. Decreasing atmospheric CO2 would be far more disadvantageous than increasing it. Methane is sourced through rice cultivation, ruminating animals, coal mining, natural gas venting, & inefficient biomass oxidation.95% of warming due to greenhouse gases comes from water vapour in the atmosphere (not water droplets as in clouds), and only 0.28% from human additions. Human activity accounts for about 6% of the non-water vapour component.  

Atmospheric CO2 levels over recent time, temperature cycle regularity and warming pulse rates 
 

The chart below displays the cyclical variations in atmospheric CO2 determined from ice core samples over the last 400,000 years, showing the ”hockey stick effect”, & the remarkable regularity of CO2 increases & reductions following 100, 000 year cycles. If CO2 causes temperature increases, what caused these regular cycles of increasing CO2 lasting about 100,000 years? If however the temperatures where cyclical (due to Milankovitch-cycle style planetary orbit, tilt and wobble variations), and the CO2 variations followed temperature changes (not driving them), this would account for this phenomena.  



A similar chart shows temperature data from Antarctic ice cores (EPICA C Dome) over the same time interval. The major warming peaks (indicated by the black arrows) are about 100,000 years apart and reflect about 8 degrees of warming. The present position on the larger zig-zag pattern suggests we are about to descend into a 100,000 year global cooling event, representing some 8-10 degrees of cooling. 


The much smaller peaks are some 1000 years apart and reflect 1-2 degrees of warming. The smaller peaks from the Greenland Ice Core data chart  ( refer to the 10,000 year Greenland ice core GISP2 chart below), show 1-2 degree, warming over 100-200 years indicating a warming rate of around 1 degree per hundred years in keeping with present warming estimates for the current warming pulse determined elsewhere by climate science sources. The consistent warming slopes on these shorter cyclical warming pulses suggest that the warming rate it fairly consistent in these 1000 year events, whose regularity suggests a very short-term (1,000 year) minor orbital cyclicity perhaps not previously recognized.  



Some 10 major warming & cooling cycles in the GISP 2 Greenland ice core are scattered regularly over the last 10,000 year interglacial warming episodes.  

Calculating global temperatures & warming & cooling rates from Greenland ice core data for warming cycles over the last 10,000 years. The warming appears generally about 2 degrees over about 200-300 year warming event. Warming & cooling appear symmetrical at about 2 degree/100 years for the higher peaks and 1 degree per 100 years for the shorter peaks. 

Other significant CO2 and temperature versus time charts across all of geological time are presented and discussed in much more detail elsewhere in this web site.

FACTS about CARBON DIOXIDE

Of the over 200 billion tons of CO2 that enter earth's atmosphere each year from all sources. Human activities—mostly burning of coal and other fossil fuels, but also cement production, deforestation and other landscape changes—emitted roughly 40 billion metric tons of carbon dioxide in 2015. Approximately 90 billion tons come from biologic activity in earth's oceans and another 90 billion tons from such sources as volcanoes and decaying land plants. According to the U.S. Geological Survey (USGS), the world's volcanoes, both on land and undersea, generate about 200 million tons of carbon dioxide (CO2) annually, while our automotive and industrial activities cause some 24 billion tons of CO2 emissions every year worldwide:
                                      www.scientificamerican.com › article › earthtalks-volca..


At 382 parts per million, CO2 is a minor constituent of earth's atmosphere—less than 4/100ths of 1% of all gases present. Compared to former geologic times, earth's current atmosphere is CO2 impoverished. During the Ordovician-Silurian glaciation (450-420 million years ago),  atmospheric CO2 was more than 4000 ppm, but did not contribute to any warming. During the Jurassic-Cretaceous glaciation (151-132 million years ago), atmospheric CO2 was more than 2000 ppm and again did not contribute to any warming. If CO2 drives climate, why were there glaciations and not a runaway greenhouse effects during these events? 


The effect of increasing levels of atmospheric CO2 on plant growth and animal health.

The photo below shows a comparison of plant growth achieved in atmospheres of differing CO2 levels. This readily displays the fertilizer effect of increased levels of atmospheric CO2. The numbers in the photo's indicate the amount of additional CO2 that has been introduced into the atmosphere, and the numbers below the total atmospheric CO2 content in parts per million.

The table and chart below display the dramatically decreasing greenhouse warming effect of increasing CO2 levels in an atmosphere, a point that is often lost when increasing CO2 levels are being discussed in the media.  The data suggests that plants are seriously starved for adequate CO2 for healthy development and optimum growth in the present atmosphere and that significant agricultural productivity may be gained in this area if atmospheric CO2 levels can be substantially increased. Optimal levels of atmospheric CO2 may be around 1000 ppm for many plant species. At present plants find it difficult acquiring sufficient CO2 from the present very thin, CO2-depleted atmosphere. 

Plants exposed to higher levels of CO2, not only grow more vigorously , they require less water (less evapo-transpiration from smaller stomata required to get adequate CO2). They can grow in drier climates and produce higher yields on smaller acreages. Limiting growth factors such as higher usage of nutrients such as nitrogen, zinc, iron etc (as exist for today''s plants) can be accommodated, as they are today, with  fertilizers, supplements and management practices. There are likely to be pros and cons, with increased CO2 levels, but plants developed and thrived under these conditions in the past, they don't need to adapt to new conditions, and they manage on less water and in drier conditions. Even the small man-made CO2 contributions over the last 50 years or so have dramatically greened the earth (see CSIRO global map below).  


The image below is derived from:  Sherwood B Idso, President of the Centre for the study of carbon dioxide and global change.  Research Physicist with the U.S. Department of Agriculture's Agricultural Research Service at the U.S. Water Conservation Laboratory in Phoenix, Arizona, where he worked since June 1967. His science citation record: as of July 2000, Dr. Idso’s research papers had been cited in the scientific literature in excess of 6,500 times, more than an order of magnitude above the norm for all scientists of that time period.

The next chart reveals in more detail the CO2 relationships shown in the infrared absorption spectra referred to earlier at the start of this section on greenhouse gases. The bar chart reveals the dramatic  incremental decreasing warming effect as CO2 levels increase, again revealing the marked lack of any significant thermal impact of increasing atmospheric CO2  above say 200 ppm. As seen in the first chart in this section, doubling CO2 from 400 to 800 ppm would have minor climate impact.  Again the world climate has nothing to fear from increasing CO2 levels further, and the converse is also true in that CO2 mitigation measures at significant cost and social impact, would also have a negligible climate impact or benefit.  These facts need to be more widely known and understood.

Climate change is not a existential threat, it is not any threat at all. There is no climate crisis, or concerns with rising atmospheric CO2 levels. We have a non-existent climate problem and a non-existent CO2 problem. We do not have to do anything at all. We could not anticipate a simpler solution. 

If it ain't broke don't fix it

CO2 & Human Health. 

CO2 is odorless, colorless, tasteless and slightly heavier than air. Plants absorb CO2 and emit oxygen as a waste product. Humans and animals breathe oxygen and emit CO2 as a waste product. Carbon dioxide is a nutrient, not a pollutant, and for all life,  plants and animals alike it is an essential requirement. Atmospheric CO2 is an essential plant fertilizer not a toxin. All animals get their carbon from eating plants, or eating other animals that eat plants. The effect of increased atmospheric CO2 on humans appears minimal at any likely concentrations, even up to 1% (10,000 ppm). Human exhale CO2 at levels of around 38,000 ppm from their lungs, suggesting that even at these levels there is no serious toxicity as long as here is adequate oxygen available for normal respiration. 

Coral reefs and CO2

CO2 gets into the atmosphere originally through volcanic eruptions.  Once in the atmosphere it is continually recycled by terrestrial plant life (through the process of photosynthesis), animal life,  the earth's oceans (in the form of the bicarbonate ion, HCO3-), and eventually into calcite (limestones, coral reef structures, marine shells & skeletons), and carbon energy reservoirs of coal, petroleum & gas.  The oceans contain more than 60 times as much CO2 as the atmosphere and are in equilibrium with marine limestone deposits. 

The great retirement home for most terrestrial carbon dioxide is in limestones (44% CO2 by weight), and they make up a considerable proportion of surface and subsurface rock sequences, including all the worlds coral reefs and entire mountain ranges in many parts of the world. Coral reefs are made of CO2 and would not exist without CO2. The coral organisms themselves derive all their cellular carbon from CO2 sourced  from bicarbonate ions extracted from the oceans, but ultimately derived from he atmosphere.


The carbonate forming chemical reactions depend on the two equilibrium reactions involved:

(1)      CO2     +    H2O      <---->   HCO3-    +     H+  (acid)      at the atmosphere-ocean interface


 (2)      HCO3-   +    Ca2+   <---->   CaCO3    +    H+   (acid)     occurring in shallow warm oceans
 
 The overall combined  reaction is:

(3)    CO2  +  H2O  +  Ca2+   <------>     CaCO3  +   2H+  (acid)   
 
Note that although these reactions are equilibrium reactions, the equilibrium strongly favors the reactions moving the the right in each case and downward in the sequence  through 1),  to 2), and the ultimate removal of all CO2 from the atmosphere, and all HCO3- from the seas, to from voluminous limestone. Eventually all the world''s carbon and all the world's CO2 will end up in limestones, (see later section), and none will be available to maintain or form any life on Earth.       

Note also that for each molecule of calcite (CACO3) produced (or molecle of CO2 consumed),  two hydrogen ions (H+,  read acid) are produced, contributing to ocean acidification.  Coral reefs themselves are responsible for much of the worlds oceans acidification, although no one is suggesting that we should eliminate coral reefs in order to reduce ocean acidification. Atmospheric CO2 when dissolving in the oceans to produce bicarbonate ions (HCO3- reaction 1 above), does increase ocean acidification, but the removal of bicarbonate ions to form coral reefs and other limestones (reaction 2 above) produces even more acid.

CO2 in the oceans and ocean acidification 

 

Carbon dioxide dissolves in the ocean to form carbonic acid (H2CO3),  bicarbonate (HCO3−), and carbonate (CO3  2−). 

 

There is about fifty to sixty times as much carbon dissolved in the oceans as exists in the atmosphere. The oceans act as an enormous carbon sink, and have taken up about a third of CO2 emitted by human activity. It has been estimated that the uptake of anthropogenic carbon since 1750 has led to the ocean becoming more acidic with an average decrease in pH of 0.1 units. 

 

No mention that coral reef formation as a major cause of ocean acidification, or that hundreds of millions of years when atmospheric CO2/acidification was much higher yet did not cause a problem. 

The pH of the ocean is around 8.0 (mildly alkaline). The introduction of hydrogen ions in the above reactions causes the ocean pH to lower and become less alkaline. It does not become more acid as the H+ ions immediately react with excess OH- ions and neutralize. Only when the pH is lowered below 7.0 will the ocean become acid and have an excess of H+ ions. Introducing H+ ions at pH 8.00 will make the ocean less corrosive (less caustic) and increasingly more neutral until pH 7.0 is reached. The use of the term ocean acidification is a misnomer until the pH drops below 7.0, which is unlikely in the present circumstances because there are enormous pH buffering reactions with geology (rocks), countering the lowering of pH to anywhere near pH 7. 

Another contributor to lowering the oceans pH is rainwater. Pure condensed water has a pH of 7.0, but rainwater has a pH between 5-6. Even compared to sea water, pure water is more acid, and rain water far more acid again. Every time fresh rainwater enters the Coal Sea from Queensland flood events it contributes substantially to ocean acidification of the reef environment. We never hear this being stated in ocean acidification discussions, or the fact that coral reef growth itself increases acidification.  


Many of the low-lying island nations concerned about rising oceans may not realize it but it is the continued growth of coral limestone and its essential CO2 component that formed their island nation in the first place and is keeping their island nations above sea level now and has been for centuries. The reactions above are ultimately responsible for all the worlds coral reefs, all the worlds limestones, dolomites and marble rock sequences  including entire mountain ranges and landscapes, all the worlds carbonate shellfish, and all the worlds calcareous soils.     

Atmospheric CO2 and climate change

Global warming began 18,000 years ago, accompanied by a steady rise in atmospheric carbon dioxide. The correlation of CO2 with temperature appears clearly demonstrated. But correlation does not always mean causation. 

What caused this phenomena is a matter of ongoing debate for some. Clearly, though, global warming and rising CO2 levels in Earth's atmosphere started long before the industrial revolution. 

In detail there are some surprising contradictions. Time lines (in the red ellipses in the diagram below), reveal that the relationships are not always synchronous or positive. 

In the highlighted red ellipses there are both positive and negative correlations between temperatures and CO2 levels which should not happen if CO2 is driving temperature. The warming rates are ten times the cooling rates and occur over much shorter periods. 

In the Vostok ice core data, if gain and loss of CO2 is the cause of warming and cooling, it is difficult to understand where the CO2 is coming from, and going to, in this period in the past on such regular cycles unless the cooling and warming episode came first and are followed by CO2 changes. The rapid warming rate versus the much lower cooling rate also is telling us something.

In this instance it appears that if temperature increases first (due to orbital forcing), followed by a delayed change in atmospheric CO2, as CO2 is released (on warming), or reabsorbed (on cooling), in the ocean. This causes an additional feedback affect on temperature with two separate pulses of temperature resulting with a recognizable delay. The temperature should be seen to increase first, followed by an increase in CO2 and further temperature feedback. .

However if CO2 levels increased first, temperatures should rise appropriate to the atmospheric CO2 concentration, (with some internal feedback) and a new equilibrium temperature would be eventually reached. There would not be two distinct pulses separated by a delay period. In this case the CO2 should be seen to increase first followed by temperature. Both this and the previous scenario can occur but should be distinguishable.
 

It appears more likely that increasing temperature in the oceans causes increased levels of CO2  to form and to be released into the atmosphere. It is well known that increasing ocean temperatures decreases bicarbonate levels in the ocean (closer to the equator), favouring more CO2 in the atmosphere and more limestone production, while at the same time lower temperature towards the poles favour increasing CO2 solubility in the oceans as bicarbonate ions (HCO3-). This means that there is an atmospheric flow of CO2 from the equator to the poles, and a counter flow of bicarbonate ions in the ocean towards the equator. On approaching the equator, as the oceans warm, some bicarbonate converts to CO2 and escapes into the atmosphere to be recirculated, and some reacts with abundant soluble Ca2+ to be permanently removed from the system in the form of limestone, including coral reefs, according to the equilibrium chemical reactions listed earlier.

Global CO2 and Temperature Across the Geological Time Scale

The extremely revealing but rather busy chart below displays the relationship of both temperature (as seen on other charts) shown in red, and also atmospheric CO2 levels (in blue), across geological time. The relationship between CO2 levels and the temperature can be seen to be totally inconsistent, varying from being a positive association, to periods where it was entirely antipathetic. 
 

During the massive decrease in CO2 over time the mean global temperature has not changed significantly, largely remaining at about 20 degrees (a few degrees warmer than at present). This is yet another demonstration (if one was necessary) that atmospheric CO2 (man-made or otherwise) has not consistently influenced global temperature at any stage in Earth history despite a massive decrease (95% reduction) and did not pose and existential threat during that period. 

 The reason that CO2 is rising is that atmospheric CO2 levels are now so low (having progressively naturally declined over 90% over earth history to present starvation levels), that the very low man-made CO2 contributions (of a few 10's of ppm/year), are now registering. This is an indication of how perilously low atmospheric CO2 actually is. We need to actively restore hugely beneficial CO2 levels by burning fossil fuels.  Global vegetation is currently starved of adequate CO2 (around 1000 ppm), for optimum growth. 


This chart in particular and the other global temperature versus geological time charts displayed in this web site, completely contradict  the popular climate change models advanced by climate alarmists  where CO2 is purported to dive temperature. 

The man-induced  atmospheric CO2 model appears to have arisen solely as there seemed no other possible explanation for observed warming. No one it seems amongst the cream of world climate science considered the possibility that it might be normal and reflected in the longer term climate history. A history that seems to have been entirely ignored .  It appears that IPCC scientists and other climate catastrophists were either entirely ignorant of this information, that has been around for more than 40 years, or chose to ignore it and not reveal it. Either way it displays an appalling lack of quality science by some of the world's leading scientists who have claimed scientific purity and superiority on this issue, howling down those with contrary views for many years. 

The second chart below displays he dramatic decline in atmospheric CO2 over he last 140 million years, down some 90% over that interval and perilously approaching the 150 ppm survival threshold for vegetation. The decline is of the order to 2-3 ppm CO2 per million years. At this rate there may be only 200 million years of atmospheric CO2 remaining. 

Why has this crucial data been missed,  or ignored in this debate by the proponents of catastrophic warming. How do the climate alarmists explain this damming data and their lack of knowledge of it?


 

What Albert Einstein said about CO2 radiative warming of the atmosphere in his 1917 paper

 
The hypothesis of global warming from man made CO2 depends on a much-repeated narrative about CO2 trapping infrared (IR) photons leaving the earth. Although a beguilingly simple idea, a host of assumptions underlie it. One of these is that the radiative photonic absorption – emission interactions of the trace gas CO2 dominate heat movement in the atmosphere. And it turns out, this argument, a pillar of the global warming theory, is false – it was refuted in advance by none other than Albert Einstein in 1917.

 In this 1917 paper:


Einstein says this about radiative heating of a gas: “During absorption and emission of radiation there is also present a transfer of momentum to the molecules. This means that just the interaction of radiation and molecules leads to a velocity distribution of the latter. This must surely be the same as the velocity distribution which molecules acquire as the result of their mutual interaction by collisions, that is, it must coincide with the Maxwell distribution. We must require that the mean kinetic energy which a molecule per degree of freedom acquires in a Plank radiation field of temperature T be

kT / 2 this must be valid regardless of the nature of the molecules and independent of frequencies which the molecules absorb and emit.”


Einstein understood like no other before or since the unity of mass, light and time. The equation e=mc^2 encapsulates this. Mass, it turns out, is a condensed form of energy not really profoundly different from photons; mass is simply anything with inertia resisting acceleration: anything that slows you down. This PBS Space-Time video illuminates this unity, beginning with a nice demonstration of how a hypothetical box of photons which should have no mass, oppose acceleration and exert inertia exactly like mass.


A nice insight from this presentation is that the “speed” c is not merely the speed of light – it is the speed of causality, the fastest speed that any cause-effect agency can transmit influence. It is fundamental to space-time and the universe’s architecture. This fundamental truth connects with Einstein’s assertion that the transfer of heat energy between photons and baryonic particles in a gas, is essentially no different from the Boltzmann transfer of heat energy from gas particle to gas particle.

The CO2 atmosphere warming story is a story that only recognizes radiative transfer of heat. It considers most of the atmosphere – all the N2 and O2 for instance – as thermally inert. This is not credible not only because of convection, which moves at least as much heat as radiation. It is because of Einstein’s insight that radiation transfer of heat to gas is a Boltzmann process just like heat transfer from one gas molecule to another. And the much-hyped issue of IR absorption frequency bands is of negligible importance – as Einstein put it, “Regardless if the nature of the molecules and independent of the frequencies at which molecules absorb and emit.”

CO2 back radiation atmospheric warming is an error that was refuted in advance by Einstein. As in other fields such as gravitation, space time and relativity, Einstein has not yet been proved wrong. He won’t be proved wrong here either. 



To access a PDF version of the original paper, copy and paste the following link into your web browser:


https://inspirehep.net/files/9e9ac9d1e25878322fe8876fdc8aa08d