Polar Stratospheric Ozone
Animation adapted from Jonathan Weiner, The Next
One Hundred Years, 1990.
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
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
Animation adapted from Jonathan Weiner, The Next
One Hundred Years, 1990.
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?
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."
Anyone who has
operated an electric train set has experienced the sharp penetrating smell of
ozone since electrical discharges in the presence of oxygen readily produce
ozone. The most common commercial technique for producing ozone is to pass
electrical discharge through oxygen as well. B. Brodie in 1872 first determined
the composition of ozone to be a triatomic molecule of oxygen.
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?
molecule adsorbed to ice crystal. Original image source,
"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
What volume does one ton of
CFC-12 occupy, in liters/ton?
The answer is at the bottom of this page.
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
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.
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
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.
"As with the greenhouse effect, feedback
may make matters worse. The dramatic loss of ozone in the hole not only lets
ultraviolet radiation pour through, but also cools the hole because the air in
the hole is losing all that greenhouse gas. Already the air above the South
Pole in October and November (springtime in Antarctica) is about 10 degrees
Celcius colder than it was in the 1970s. The less ozone there is in the hole,
the colder it gets, and since more ice crystals form as it cools, the colder
the hole the less ozone there will be. The hole is lasting longer and longer as
it grows colder and deeper. The final warming, the break-up of the hole, is
coming weeks later in the austral spring than it once did. That means the
living creatures down below are being exposed to higher levels of UV for a
longer period of time."
"If predictions are correct (and they
have been), the greenhouse effect will chill the whole stratosphere by
another ten degrees Celcius during the next fifty years, putting even more ice
crystals up there. That could(will) lead to bigger holes at the North and South
Poles. Already the North Pole is loaded with chlorine compounds from CFCs--
Robert Watson, of NASA, who oversees each Hole Expedition, says arctic
stratospheric chemistry is in a state of "incredible perturbation."
"The ozone crisis makes the rise of
methane in the atmosphere much more alarming, because when methane breaks
apart, one of the by-products is water vapor."
Jonathan Weiner, The Next One Hundred
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
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.
3D Keeling curve. Save either image.
Largest-ever ozone hole observed over Antarctica,
Largest-ever ozone disappearance observed over the
Arctic, 2000. NASA.
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
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
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, your
light's on. Is anybody home?
Earth to NASA, come in
The texture image for the Jonathan
Weiner animated gif is from photo by Jerry Bauer.
"Therefore I charge you, should you ever
Other accounts of this, to let no falsehood
Confuse the truth which
I have just made clear."
Jonathan Weiner quoting Dante from Canto Twenty
of the Inferno.
A ton of CFC-12,
dichlorodifluoromethane, as the sole gas in a closed system at STP, would
occupy a volume of about 168 thousand liters. In general, to find the volume of
a gaseous compound at STP, divide the number, 20,339,200 by the molecular
weight of the gas in grams. The result will be in liters per ton.
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.
Volume 2, Applications
Edited by Philippe Renaud and
Mukund P. Sibi £ 210.00 $ 360.00 DM 760.82 Wiley-VCH, pp 1162 Hardback
Exerpt from the *Alchemist Book of the Month
"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
*Registration as a Chemweb member is required
to visit this site.
"Who gives a
hoot about habitat?"
For web searches on this subject we