Guest Post by Richard F. Cronin
August 3, 2017
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.
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.”
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.
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.
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).
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.
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.