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Polar Stratospheric Ozone
Ozone Loss over Antarctica, monthly averages for october and TOMS images from 1980 to 1991. University of Cambridge.http://www.atm.ch.cam.ac.uk/tour/part2.html "In fact the change in the air and in sunlight in the next few decades may pose more danger to animals and plants than to human beings. Laboratory tests show that UV-B can damage fish, shrimp, and crab larvae, copepods, krill, and the zooplankton and phytoplankton at the base of the food chains in the sea. A 10% increase in UV killed almost all (phytoplankton) specimens. Since the Ozone Hole is going to be with us for at least one hundred years, we could cause an evolutionary upheaval if thousands of species in the sea weaken and others more resistant to these rays take over. The billions of krill in Antarctic waters - which are shrimp-like crustaceans - depend on the phytoplankton. Baleen whales, sperm whales, squid, seals, the albatross and the penguin are among the many creatures that depend on the krill. El-Sayed (researcher) suspects that krill may be among the first casualties of the Ozone Hole. 'If anything happens to the krill,' he has said, 'the whole ecosystem will collapse. We can say good-bye to the whales, to the seals, to the penguins, et cetera.'" Jonathan Weiner, The Next One Hundred Years, 1990.
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Phytoplankton, zooplankton. Krill? Fish, whales, penguins, seals. Since Mr. Weiner's book was published in 1990, it had been widely reported in the mid and late 1990's that 90% of the krill in Antarctic waters had disappeared. Web searches for krill these days turn up a conspicuous lack of information. A dry well. Very close to zilch. In 2001 penguins from the Antarctic began arriving on the beaches in Rio de Janeiro. It was not a regular migration. It has never happened before. Penguins were forced to make the swim of several thousand miles because there is a severe lack of food source in their native habitat. This development is particularly ominous for baleen and sperm whales which are more directly dependent upon the krill. Instead of eating the fish that eat the krill, they eat the krill. The general media has yet to report a clear linkage of these events. They are probably trying to find some way to put some kind of spin on it which will allow for the preservation of the illusion that the earth has not been overpopulated by humans. The penguins couldn't wait to see what kind of spin was put on the story. The lack of antarctic stratospheric ozone is causing severe biotic damage already, not at some time in the future. This is an example of ecological predictions by scientists which have come true much sooner than publicly stated because their original predictions had been intentionally conservative. The scientists had not wanted to be seen as alarmist. Similarly, the north polar ice cap was found to have melted through in 2000, fifty years ahead of schedule. In all likelihood the large Antarctic ice shelf will break off far ahead of schedule as well. |
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As can be seen from the way the ozone hole has developed, the damaging effects of the sun's UV radiation has spread from the inland ice pack where it had virtually zero ecological imapct, to the periphery of the Antarctic where it causes profound ecological damage. The peripheral areas of Antarctica are the places which are now experiencing the most damage to biodiversity because the various life forms which are damaged by UV are concentrated there. From the image above it can be seen that the blue area, the extent of the ozone hole during the most critical two month period of the year for the affected life forms, includes the edges of Antarctica and spreads outwards for hundreds of miles. In this critical area the UV radiation pours down through the atmosphere unimpeded by the once-protective ozone. The opportunity for conservation of whale, seal, or penguin numbers as a means of preserving the illusion that humans have not overpopulated the planet may have passed. Damage to the photosynthesizing phytoplankton or to the zooplankton is most severe because they are the most vulnerable to UV. Krill down by 90%. Some spinmeisters say it ain't so. How long can they continue blowing that smoke? Hellooo. Your light's on. Is anybody home? |
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Ozone. Ozone is slightly soluble in water, has a
molecular weight of 48.000, has a specific gravity of 1.658, and a boiling
point of -112 degrees Celcius. As a gas ozone has a light blue color. As a
liquid, it is deep blue in color and very explosive. Ozone is a strong oxidizer
as it wants to give one of its oxygens to just about any other molecule or atom
which will even lightly accept it.. Ozone was first named in 1840 by C.F.
Schonbein from the Greek verb, ozein, "to smell." The chemistry of ozone (and indeed of the other small molecules involved in greenhouse and other phenomena of critical ecological importance) is so well known, so basic, and so fundamental that relatively few new students of chemistry had initially considered them as subjects for specialized study. In fact as the planetary ecological crisis had developed to its current absurd proportions, specialization in the study of ozone may have been undeservedly considered a sign of either intellectual weakness or pedantism, simply because the term ozone had been widely popularized. Ozone has been routinely used for decades to introduce the concepts of molecular orbitals, resonance forms, and radical chain mechanisms to first year students of organic chemistry. Advanced students of organic chemistry and research chemists have used ozone in ozonolysis, a reaction used in organic chemistry as part of a process to determine the structures of olefins, unsaturated hydrocarbons containing double bonds. Chemical engineers are familiar with ozone in a plethora of commercial applications where as a powerful oxidizer it is used as an antiseptic and a bleaching agent. Scientific understanding of ozone is not new. Perhaps scientists have a somewhat larger view and an enhanced appreciation of ozone in the earth's atmosphere where it plays a crucial geophysical role. But this role has been so intensively researched in the last several decades that our knowledge of it has virtually no important gaps. The ozone holes at the poles and particularly at the Antarctic pole are plainly visible. In fact the Antarctic hole has become so large, more than three times the size of the continental United States, that it would be easily discernable from the planet Mars with the proper photographic filters.
President Bush's declaration on his first official trip to Europe that our thorough scientific understanding of the scientific principles related to the ecological crisis is, "Just not scientific," is not an indication of intellectual weakness on the part of the American president. Obviously his words belied the truth. President Bush demonstrates a keen understanding and a utilization, ben trovato, of one of the most dangerous realities of modern life. Most persons in both Europe and America are scientifically illiterate. A fact which he is able to use to great personal advantage repeatedly. Ozone? Ozone-schmozone, right? |
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"Ozone is a greenhouse gas, and when it descends to the troposphere, which is denser, its greenhouse effect becomes stronger. Already ozone's effect on the atmosphere of the planet has become about one-sixth as great as carbon dioxide." "in the coldest parts of the stratosphere this water vapor tends to form tiny ice crystals. The ice crystals as they drift through the stratosphere collect the stray atoms of chlorine from the shattered chlorofluocarbons. Many chemical reactions are strongly promoted by the presence of solid surfaces, and a chlorine atom on the surface of this ice can eat many thousands of times more ozone than a chlorine atom adrift." "In september, 1987, at an historic international convention in Montreal, negotiators from most of the world's major industrial nations signed a treaty to slow down global chlorofluorocarbon production. However, more of the compounds are still being made. One year after the signing of the treaty, CFC-11 and CFC-12 were still accumulating at a rate of about 5 percent a year. CFC-113, which is the best solvent for cleaning computer microchips, was increasing at 11 percent a year. They were by far the fastest increasing of the greenhouse gases. Carbon dioxide is increasing at a little less than half a percent per year. And nothing can be done to remove the millions of tons already released into the atmosphere since 1930, including the Freon in the breath with which Midgley triumphantly blew out the candle. These chemicals will continue to drift into the stratosphere. They will go on eating ozone and magnifying the greenhouse effect for more than a century." The spray can ban had not really cleared the air, of course. The global production of CFCs never actually decreased very much. After the ban, the U.S. chemical industry simply diverted its production of CFCs from spray cans to coolants, foamers, and cleaners. Other countries went on putting CFCs in spray cans-- and made more spray cans than ever. World production probably shrank a little in the late 1970s, but by the late 1980s it was rising again. The world manufactured more than a billion pounds (500,000 tons) of CFCs in 1988. By then there was six times more chlorine in the atmosphere than there had been at the turn of the century." Jonathan Weiner, The Next One Hundred Years, 1990. Question: |
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Radical Halogens
A radical is anything which contains an unpaired, unshared electron. All halogenated hydrocarbons, halocarbons, can be split into radicals by the photochemical action of UV radiation. The catalytic activity of each of the resulting halogen radicals is such that each is readily able to split ozone. Much emphasis has been placed on chlorine radicals formed from CFCs. As other halogenated compounds are substituted for ones currently commonly produced, one must also consider that the radical forms of fluorine, bromine and iodine are catalytically destructive of ozone in a manner which is identical mechanistically. The catalytic activities vary and are less than that of the chlorine radical. The initial drastic depletion of ozone from the stratosphere over several decades as well as the formation of crystalline ice surfaces in the stratosphere during the same time period mean that even the halogenated compounds used as substitutes will not solve the problem of ozone depletion. Ozone is an unnatural or at least, unusual molecule. It is actually thermodynamically unstable. Ozone does not want to be ozone. Two molecules of triatomic ozone would much much rather be three molecules of diatomic oxygen. The molecular orbitals of ozone form strange and constantly changing resonating forms as the three atomic nuclei do their best to try to share the mismatched compliment of electrons. That is why a halogen radical splits ozone so readily. When ozone levels have become one tenth the starting level, the catalytic halogen molecules' concentration will have increased a hundred fold. Rapid increases in methane gas will have led to crystalline ice stuctures as well, especially in the stratosphere above the poles. Ice is increasing in the polar stratosphere where it enhances the catalytic power of chlorine by a factor of several thousand. The possibility of oxygen reforming the thermodynamically precarious triad, ozone, will have become remote. Some highly reactive halogenated compounds which participate in the radical chain reaction mechanisms which break down ozone started to be phased out just at the end of the 20th century. Production of certain halocarbons was stopped in industrialized nations. The production was continued in other countries. Humans finally woke up and drastically reduced certain halocarbons used as refrigerants and aerosol sprays. That was a nice first step. Although it was a baby step, it was in the right direction. And world leaders had to be dragged kicking and screaming to the bargaining table. Other halocarbons were substituted for the ones whose production had been reduced. Many more halocarbon compounds are in production. It may be true that humans can find substitutes for halocarbons. Thus far however, humans have substituted some halocarbons with other halocarbons. Numbers of humans, the diverse number of halocarbons and overall halocarbon production to satisfy the needs of humans has increased. And the stratospheric ozone hole has become a large and permanent feature of polar meteorology. The ozone hole has steadily incresased in size and will continue to enlarge, even if humans substitute some halocarbons for other halocarbons.
Stratosphere The stratosphere is where ozone functions to reduce UV radiation. Halocarbon compounds which have been released into the atmosphere thus far have not yet reached the stratosphere. The peak concentration levels have yet to be reached in the stratosphere both globally and at the poles. Halocarbon effects do have a decay curve. That curve is measured in many decades. If halocarbon production were completely halted tomorrow, humans could count themselves lucky if concentration levels peaked in a decade or two. The probability that that will happen is low. Halocarbon production will not stop tomorrow. They are indispensible for too many processes which make a high technology life style possible. Human numbers are increasing exponentially. Furthermore, every effort is being made to globalize the convenient high technology lifestyle. What does this mean? It does not mean that convenience is bad. Nor that high technology is bad. Nor that poor people shouldn't have cars, houses, TVs, refrigerators and toilets. Although that is how these sorts of statements in combination with the HOP word are routinely misinterpreted. What this does mean is simply that peak stratospheric halogen concentrations are not within sight. It means that the situation is bad. The situation will get worse. And it will be a long, long time before it gets better. It won't even begin to get better until the human population comes down. Ozone is needed in the stratosphere, especially at the poles. Even after peak halogen concentration levels have been achieved, many decades from now, ozone will not be restored suddenly. Not even. The radical chain mechanisms by which halogens break down ozone are catalytic in nature. An atomic chlorine radical, for example, breaks down thousands of ozone molecules. It doesn't stop until it bumps into nitrogen. Only a millionth part of the stratosphere is ozone. It's amazing that molecules measured in parts per million, billion, or trillion, should matter to such a big planet. If all the ozone in the atmosphere were spread out on the ground it would form a layer about as thin as a piece of canvas. That's not very much. The thinner the ozone layer in the stratosphere becomes, the higher the ratio of catalyst to substrate. Under conditions of excess catalyst, the equilibrium for halogen initiated radical chain reactions with ozone will lie far to the product side. As more and more halogen compounds reach the stratosphere, conditions of excess catalyst merely become conditions of super excess catalyst. There is a feedback loop for increasing the
ozone destruction and keeping it that way at the poles. Ozone, even at the
minute parts per trillion levels found in the atmosphere above the Antarctic,
had previously been adequate for warming the polar stratosphere sufficiently to
prevent the build up of ice crytals.
Conditions of excess catalyst become conditions of super-excess catalyst for halogen radical based elimination of stratospheric ozone. This destruction will be increased and worsened by several factors of ten as stratospheric ice formation increases. Ice surfaces increase catalysis of radical halogen based ozone destruction by factors from hundreds to thousands. The ozone hole in the stratosphere above the Antarctic is a large and permanent reality now. It is not some hypothetical product of a gloomy doomy mind. It is real. It is tangible. It is measurable. And it has reduced the krill by 90%. That is very bad news. It is just one more prediction which has come true far sooner than had been conservatively estimated. The social milieu is characterized by pervasive, apalling and frightening scientific illiteracy. |
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3D Keeling curve. Save either image. |
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NASA, once in the vanguard leading the cause for ecological awareness, many believe has become a tool for downplaying the severity of the ecological crisis. We believe the presentation by NASA of imagery informing mankind of the progress of ecological destruction could well stand improvement. The pathetically insufficient efforts of NASA to keep humans informed of the extent of damage to the biosphere of planet earth have been described as a, "stonewalling whitewash." It is notable that NASA announced in late August 2001 that an important satellite monitoring ozone would be discontinued since the piddling cost of ten million dollars has been labelled excessive. Just when the information the satellite could provide is needed more than ever before. It makes you wonder just what the heck their priorities really are. By far one of the most powerfull tools for obtaining the necessary scientific information and at a time when the need is more critical than ever before. And so what do they do? They just say, "Oh, well. We don't need it anymore." Which is more important, the information, or the lack of it. One may wonder just what is on their agenda. NASA possesses the most powerful of all conceivable tools available for monitoring the insidious processes of islandification and biodiversity decay, the atmosphere of the planet, the condition of the hydrosphere, the deforestation of the land, and the fires which burn incessantly day after day after day. They produce images by the hundreds on a daily basis from both geosyncronous and circularly orbiting spacecraft, each and every day, seven days a week, 365 days a year. And yet relative to NASA's powerful ability to present images of this destruction images are extremely few in number, not organized into meaningful categories, and exceedingly hard to find. There is no centralized location for them. In fact, the live webcam which had showed the exact locations of fires burning in the tropics has been discontinued. It is as if NASA had the world's largest virtual cannon with which to deliver a knock out blow to a large and terrible menace. But instead it chooses to use the equivalent of a BB gun. True, one may find the odd environmental image or two here and there. But one may find just as many images of hurricanes and typhoons. Every chunk of ice the size of Rhode Island which has broken off and floated away from Antarctica has been photographed. Are the images online? Can they be located? Are they described in their ecological context? Maybe, but probably not. Maybe, but probably not. And no. In that order. Compared to what NASA could be doing and should be doing, their effort is at best, perfunctory and pathetically insufficient. The most important category of NASA images should be a large, well categorized, centrally located and easily accessible collection which depicts and describes every visible change in earth's biosphere. The resolution which is possible is now in fractions of meters. Understandably, due to security considerations the publishable images must have lower resolution. But they should be much more well organized and presented for preservation of biodiverse life forms. And helping humankind, too.
Earth to NASA, come in
please!? |
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"Therefore I charge you, should you ever
hear Answer: |
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A Buddycom member wrote in asking, "Are radicals bad or dangerous?" This gave us a chuckle. No, radicals can be quite useful in organic chemical synthesis. Consider this book of the month from *Chemweb.com. It's rather pricey at $360 for the multivolume set, but well worth the expenditure.
Exerpt from the *Alchemist Book of the Month review: "For chemists, if not for biochemists, the 'free' in the title of the double volume 'Free Radicals', edited by J.K. Kochi and published by Wiley in 1972, has long since been dropped. But in those two volumes were laid down the ground rules of modern radical chemistry. Nevertheless, it was another decade and a half before organic chemists began to recognise that the kinetic behaviour of radicals, when they were generated in carefully tailored systems, could furnish complex products with a selectivity and efficiency which was a match for the best that ionic reactions or other more familiar methodologies could offer. The literature relating to synthetic applications of radical chemistry has snowballed during the closing years of the 20th century, and Renaud and Sibi have embarked on a timely project to collect and collate the major developments. Careful thought has been given to the organisation of topics covered, with forewords by Bernd Giese (Vol. 1) and Dennis Curran (Vol. 2) setting the scene. Many of the 76 (!) contributors are leading workers in the field, and the result is two beautifully produced volumes which should most certainly find their way into every laboratory where organic synthesis is practised. And for such a multi-author work, there is remarkably little evidence of duplication of material between contributions." *Registration as a Chemweb member is required to visit this site. |
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