The Myth of Man-made Ozone Depletion

Written by Richard F. Cronin

After 31 years working for E.I. DuPont de Nemours here is my understanding about “ozone depletion” — the warm-up act for anthropogenic CO2-induced “global warming”. Even the proponents of human-induced “ozone depletion” are starting to realize that the thinning of the ozone layer is a natural phenomenon that just waxes and wanes.

Ozone (O3) is produced in the stratosphere by the intense solar radiation causing photo-dissociation of the di-atomic oxygen molecule (O2). The oxygen singlet (- O) is a powerful oxidizing agent and readily reacts with another O2 molecule to yield ozone. Ozone is not produced during the dark polar winters and its lowest point is in the early spring. The ozone layer is renewed by the sunlit polar summers.

Molina and Rowland published in 1974 and their core premise is that heavier-than-air chloro-fluoro carbons (CFCs) convect upwards using a “one dimensional diffusion model”, where they photo-dissociate due to ultraviolet radiation in the band of 2000 Angstroms to yield ozone -destroying chlorine and bromine. Molina and Rowland also stated that CFCs do not dissolve in water, so they are not scrubbed out by rain at lower elevations. However, it is known that organo-halogens adsorb on dust particles and aerosols which are scrubbed out by rain in the troposphere. Finally, volcanoes emit CFCs as well as copious amounts of hydrofluoric acid (HF), hydrochloric acid (HCl) and hydrodrobromic acid (HBr) which carry up to the stratosphere. (Ian Plimer, et al). See “Heaven and Earth” by Ian Plimer, University of Adelaide. There is always some equilibrium presence of these molecules, in trace quantities.

http://onlinelibrary.wiley.com/doi/10.1029/RG013i001p00001/full

Click here for Atmospheric aerosols in the Earth System

Quoting from references at Berkeley – University of California:

“Molina’s research pointed to just one possible fate for the CFCs: they would remain in the atmosphere for a long time — somewhere between 40 and 150 years — before they drifted high enough for solar radiation to split off a highly reactive chlorine atom from the CFC molecule. This chlorine atom could then react rapidly with ozone, destroying the ozone molecule and depleting the ozone layer. Molina’s hypothesis consisted of three main points, each requiring its own tests:

CFCs break down to produce chlorine. Scientists can recreate the intense solar radiation found in the upper atmosphere in their labs. Shining this lab-made solar radiation on CFCs and then looking for chlorine would provide evidence either for or against this idea.
Chlorine atoms destroy ozone. Finding chlorine atoms and the products of the chlorine-ozone reaction in the ozone layer would support this idea.
This is causing significant ozone depletion. The validity of this point could be examined by analyzing worldwide atmospheric ozone levels over time. Since CFCs remain in the atmosphere for so long before they break down, the effects might not be immediately measurable, and many years’ worth of monitoring might be needed to see how ozone levels are changing.”
http://undsci.berkeley.edu/article/cfcs_checklist

This final test is the sticking point for CFCs being long-lived in the upper atmosphere. Observations have been made since 1987 and the Antarctic “ozone hole” just waxes and wanes. Moreover, the industrialized regions of the Northern Hemisphere are logically the greatest emitters of CFCs, so why isn’t the Arctic “ozone hole” more pronounced than Antarctica ?

Antarctica has a larger “ozone hole” (actually it’s a thinning) due to emissions of Mt. Erebus and the southern volcanoes of Chile, like Mt. Calbuco. Moreover, the powerful circumpolar winds circling Antarctica effectively seal off the South Pole from ozone that has been produced in the sunlit regions of the mid-latitudes during the Antarctic winter. The circumpolar winds relent in the spring and summer, allowing mid-latitude ozone to leak into the Antarctic.

The volcanoes of Iceland influence the chlorine and bromine presence in the Arctic, but less than the Antarctic. The Arctic does have a polar vortex, but nothing like the circumpolar winds of Antarctica. Ergo, there is continuous leakage of ozone produced in the northern mid-latitudes into the Arctic.

Another natural phenomenon affecting the ozone layer is the inversion of the geomagnetic field at the polar regions which exposes the ozone layer to the ionized solar wind and coronal mass ejections (CMEs). The power of this ionized stream is observed in the aurora borealis. Ozone is ripped off by the tons and tons. Any activity of trace CFCs, chlorine or bromine is dwarfed, although the halogens are the variable actors.

DuPont argued the issue about the Freons@R until the 1980s and finally realized that they had been tried and convicted in the court of public opinion. Ergo, DuPont management figured: “Why fight ’em ? Join ’em”. So DuPont jumped on the band wagon, shed the perfectly innocuous and efficacious Freons@R, and threw the Company behind the 1987 Montreal Protocol.

DuPont, ICI, and Allied Chemical (now Honeywell) had an oligarchy in the “ozone depletion substitutes”. Great PR, brand new captured market, govt support, and a relaxed schedule to make the conversion to the substitutes. Not only the Freon@R substitutes, but a large market in custom lubricants for new “ozone friendly” refrigeration equipment. Freon@R and most of the old Freon@R compounds are compatible with mineral oil.

Now the schedule mandated by the Montreal Protocol decrees that refrigerants must be entirely “chlorine free”. The only substitutes are fluorinated compounds which are entirely stable under solar radiation. The new refrigerant for automobile air conditioners is R-1234yf, far more costly than the current R-134a, with EPA tradeable credits as an offset (taxpayer dollars). Although stable to solar radiation, R-1234yf is toxic and can be flammable. A ruptured air conditioning reservoir would be exposed to the hot engine. Daimler, Volkswagon, and BMW are reluctant to use it in their automobiles and are opting for CO2-based refrigeration.

http://www.autonews.com/article/20131230/OEM01/312309996/automakers-switch-to-new-refrigerant-will-accelerate-with-epa-credits-

The 1987 Montreal Protocol is entirely self-reporting and nobody can audit anything (just like Anthropogenic CO2). The only countries that nominally comply are the U.S., Canada, the EU and Australia (?).

All the refrigeration equipment based on the original Freons@R was ripped out and sold around the developing world. They still run, supplied by China, Eastern Europe, India and just about every other nation with an industrial chemicals capacity. The majority of air conditioning units in the U.S. are “dry shipped” to be filled with R-22 by a “licensed contractor”, allegedly from “recycled R-22” inventories.

http://www.energyvanguard.com/blog/55282/HVAC-Secret-An-Air-Conditioner-Loophole-the-Size-of-the-Ozone-Hole

You can buy carbon tetrachloride and all the old Freons@R on e-Bay or Amazon, allegedly from “recycled” sources. There are no substitutes for Halons@R used for fire suppression on aircraft and data centers, yet we never seem to run out. Carbon tetrachloride is deemed to be only “man-made” like the CFCs and is banned under the Montreal Protocol but carbon tetrachloride is emitted by the gigaton from volcanoes, hydrothermal vents and weathering biomass (Gordon Gribble – Dartmouth, see link).

https://www.ebay.com/sch/i.html?_nkw=freon+12

http://www.springer.com/us/book/9783211993224

Of course, most recently, the Antarctic “ozone hole” has been “healing” somewhat. Even those who believe that human existence and technological betterment must be sharply curtailed — acknowledge the quieting of Chile’s Mt. Calbuco had “something” to do with it, but mostly they repeat the mantra that thru concerted national cooperation under the Montreal Protocol we have saved the world. Man’s industrial efforts are still deemed to be the causation of any undesired variations in the planet’s biome.

http://science.sciencemag.org/content/353/6296/269

No one in the scientific community dare rebuke the “received wisdom”. If they do so, they are ostracized, lose tenure, shut out of grant funding, cannot be published in mainstream science journals, and declared to be co-conspirators in destroying the planet. Open source publishers in China (MDI), India (OMICS International) and the developing world have surpassed traditional western science publishers. Indeed, the western science community has been subject to a new version of the McCarthy Red Scare, complete with deliberate intimidation.

But — Whooo-hooo !! Now we have defeated Chlorine and Bromine. We have “saved the ozone layer”. Now onto the war on Carbon !!

If you declare war on elements of the Periodic Table, you gonna lose.

Read more at: cbdakota.wordpress.com

Comments (5)

  • Avatar

    K. Kaiser

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    … and as it so happened, when the “cause” of the ozone-hole was ascribed to the Freons, DuPont had just patented the new “much safer” HCFCs. By now, the patent protection for those have run their course too and, naturally, DuPont has now even “safer” substitutes.
    It is a travesty and tragedy how false claims and wishful thinking often produce the opposite environmental effects of what their proponents claim.
    The war on the elements of Periodic Table is just warming up.

  • Avatar

    Joseph Olson

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    “Volcanic Halocarbons” by Timothy Casey at Geology-1011 website

    Fluorine is the sixteenth most common element and constantly emitted by volcanic sources. Some Ozone is produced by solar ionization, most by lightning with hundreds of strikes per second. DuPont patents expired on Freon so they supported the Montreal Protocol, the beta test for CO2 demonization. Ozone has been used as a safer, more effective water treatment than Chlorine in Paris, and two thousand cities for over a hundred years. Groundlevel Ozone absorbs the same cancer causing UV as Tropospheric Ozone. There is NO asthma bacteria, virus or even a disease, only a weaponized EPA canard for cost/benefit studies.

    We have been systematically LIED TO ABOUT EVERYTHING.

    • Avatar

      Richard Cronin

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      Thanks for the kind words, Mr. Olsen. I am very proud of my years in DuPont and when pressured by Government and an unthinking public, what is one to do ? Go out of business ? That certainly would be entirely satisfactory for Greenpeace , academics who have no real world experience, and unaccountable publishers. “Peer Review” is the “buddy system”. The essence of the Scientific Method is independent replication. It is employed in the breach. Again, thanks for your words, yet I would contend that the managers of DuPont who I knew were moral men and women trying to do their best against larger forces.

  • Avatar

    jerry krause

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    Hi Richard F. Cronin and PSI readers,

    Richard, thank you for introducing this topic which has long needed a closer look. And my comment is directed to what you wrote because few others have invested the time trying to better understand the dynamics of the atmospheric ozone system. 31 years ago is about 1986. In the 1970s I, as a chemistry instructor, was teaching about the ozone hole being observed to occur over the Antarctic continent during September, the spring season there. I was teaching about a topic—atmospheric science—which, as a chemist, I had never studied. So, I was attempting to learn about what I clearly did not know and I was communicating by telephone with Dupont’s scientific spokesperson about what was known about this phenomenon when Dupont did their beneficial flip-flop. So, I have pondered this system much longer than 31 years and even because of your article I have seen something which I had not really seen before.

    The division of the atmosphere by its temperature is well known and discussed because of the stratosphere’s temperature inversion (the atmosphere’s temperature increases with increasing altitude instead of decreasing as it should because the action of the earth’s gravity upon the tiny masses of the tiny atmospheric molecules). The now well known cause of the stratosphere’s temperature inversion is due to the certain u-v photons of solar radiation which dissociate oxygen molecules and ozone molecules. This photochemistry is the focus of your article and the reason I was teaching about an atmospheric phenomenon in my introductory chemistry courses.

    However, I cannot find much attention being given to two other well and long accepted divisions of the atmosphere—the homosphere and the heterosphere. The cause of these divisions is the action of the earth’s gravity upon the tiny atmospheric particles differing masses. “By itself, gravity would turn the atmosphere into a layer cake with the heaviest molecules near the Earth’s surface and the lightest molecules at the top of the atmosphere. However, weather processes ‘stir’ the atmosphere, helping to keep it well-mixed almost to its out edge. (Meteorology 3rd Ed., Steven A. Ackerman and John A. Knox) These authors previously had written: “The molecules of gases and liquids are in constant motion. They naturally spread or diffuse from areas of high to low concentration.” They then asked the question—“If our atmosphere is an area of concentrated molecules, than why don’t they eventually diffuse into empty space?—to which we have already considered the generally accepted answer—gravity.

    Ackerman and Knox, in their meteorology textbook, never wrote the words homosphere and heterosphere nor did they ever address the weather processes which kept the atmosphere “well-mixed almost to its out edge”. Which, the edge, is commonly stated by others is at an altitude from 80 to 90 km.

    This is not the place to describe this oxygen-ozone-radiation atmospheric system in detail but chemists now consider, which originally was not considered, that the reaction of an oxygen atom with an oxygen molecules to produce a stable ozone molecule requires a three-body collision instead of the much more frequent collisions between only an oxygen atom and an oxygen molecule. The third body is required carry away excess kinetic energy which would immediately dissociate the ‘excited’ ozone molecule formed during the common two-body collision. And it is by this mechanism of the three-body collision that the kinetic energy of the stratosphere is increased (hence its temperature increased).
    What I have finally seen (or understood) is the altitudes of the maximum ozone content of the stratosphere or the altitude of the stratosphere. For at the tropical latitudes the altitude of the stratosphere is the greatest and it steps down to a lower altitude in the mid-latitudes and is found at the lowest altitudes in the polar latitudes.

    My previous problem was I could not understand (explain) these altitude distributions of ozone. I knew that Newton considered the centrifugal effect of the rotating earth as he calculated the now observable ellipsoid shape of the solid earth instead of a spherical shape if one only considered the influence of gravity. I was assuming that the density of the atmosphere at say, 15 km, over the polar area was the same as that over the equatorial area at the same altitude. I did not assume, and obviously did not have the skill to calculate, that the atmosphere has even a more ellipsoid shape than the earth beneath it. Hence, the altitudes of maximum ozone density are near the same atmosphere density even though these altitudes are quite different.

    I ask you, Richard and others, to consider what I have considered and to report here what you have concluded.

    Have a good day, Jerry

    • Avatar

      jerry krause

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      Hi Richard,

      Have discovered that you are not likely reading my comments because I have just discovered that your article was a guest posting at cbdakota’s site.

      Richard asked— so why isn’t the Arctic “ozone hole” more pronounced than Antarctica?—and gave his reasoning for this observed fact. He reviewed observations to support his reasoning so I cannot be critical of his reasoning. But I consider that the extremely different topography of the two polar regions might have something to do with some differences between them.

      I read that the Antarctica continent has an average elevation of 8200 ft and an area of 5.4 million square miles. The Arctic polar region is primarily ocean; so its average elevation is about 0 ft. Hence, the northern polar region has a greater atmospheric volume of about 8 million cubic miles. And since the density of the atmosphere increases as the its altitude decreases, the difference in the masses of the two atmosphere’s over the two polar regions is even more significant.

      But maybe these factors (differences) are not the most important. He referred to the circulations of these atmospheres but he did not mention the drainage of the necessarily cold, hence dense, surface layer of the atmosphere away from these two polar regions. Because of the elevation differences, I must conclude that the Antarctic drainage is aided by gravity and if gravity plays any role in the drainage of cold, dense, air from the northern polar region, it hinders this drainage because of the higher elevation landmasses which nearly surround the Arctic Ocean. As there are only two or three (Hudson Bay) outlets which do not require the atmosphere gain elevation in draining away from the central polar region.

      Now, old time grain elevator operators know that the last grain they put in a bin, is the first out when it is drained, via the action of gravity, through a small central hole in the floor of the bin. So I consider the meteorological mechanism which mixes the atmosphere so it has a uniform composition (homosphere) of nitrogen, oxygen, carbon dioxide, and argon up to the less than sharp boundary between it and the hetrosphere is the action of gravity upon these molecules and atoms. Or, stated a bit differently, a subsiding column of atmosphere is not influenced by any temperature gradients which might be found in the column because a temperature gradient can never invert the atmosphere’s density gradient.

      I could go on about the further details I could imagine as occurring but I consider them only perturbations upon the central principle involved. Somehow, maybe everywhere but in a column of subsiding atmosphere, molecules and atoms are diffusing upward in the stratosphere and mesosphere to replace those moving toward the subsiding column. And, of course, the atmosphere in this subsiding column is being adiabatically warmed as it descends and becomes more dense.

      Have a good day, Jerry

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