Thursday, December 15, 2011

CFC fraud

Popular saying: "Man is the only animal that trips twice on the same stone"

Although we are not animals, we can become like beasts.

Only ignorants ignore history. Not learning from errors, means repeating them.

Remember the CFC psychosis on the ozone layer? It was all a fraud! Just like the climate change.

Chemists poke holes in ozone theory

Reaction data of crucial chloride compounds called into question.

The hole in the ozone layer (blue) over Antarctica results from chemicals such as CFCs.The hole in the ozone layer (blue) over Antarctica does not necessarily result from chemicals such as CFCs.NASA/AP
As the world marks 20 years since the introduction of the Montreal Protocol to protect the ozone layer, Nature has learned of experimental data that threaten to shatter established theories of ozone chemistry. If the data are right, scientists will have to rethink their understanding of how ozone holes are formed and how that relates to climate change.
Long-lived chloride compounds from anthropogenic emissions of chlorofluorocarbons (CFCs) are the main cause of worrying seasonal ozone losses in both hemispheres. In 1985, researchers discovered a hole in the ozone layer above the Antarctic, after atmospheric chloride levels built up. The Montreal Protocol, agreed in 1987 and ratified two years later, stopped the production and consumption of most ozone-destroying chemicals. But many will linger on in the atmosphere for decades to come. How and on what timescales they will break down depend on the molecules' ultraviolet absorption spectrum (the wavelength of light a molecule can absorb), as the energy for the process comes from sunlight. Molecules break down and react at different speeds according to the wavelength available and the temperature, both of which are factored into the protocol.
Cl2O2 is key to ozone (O3) depleting reactions such as this one, in which photolysis results in a chlorine radical (Cl•) that reacts with O3.Cl2O2 is not key to ozone (O3) depleting reactions such as this one, in which photolysis results in a chlorine radical (Cl) that reacts with O3.
So Markus Rex, an atmosphere scientist at the Alfred Wegener Institute of Polar and Marine Research in Potsdam, Germany, did a double-take when he saw new data for the break-down rate of a crucial molecule, dichlorine peroxide (Cl2O2). The rate of photolysis (light-activated splitting) of this molecule reported by chemists at NASA's Jet Propulsion Laboratory in Pasadena, California1, was extremely low in the wavelengths available in the stratosphere — almost an order of magnitude lower than the currently accepted rate. “This must have far-reaching consequences,” Rex says. “If the measurements are correct we can basically no longer say we understand how ozone holes come into being.What effect the results have on projections of the speed or extent of ozone depletion remains unclear.
The rapid photolysis of Cl2O2 is a key reaction in the chemical model of ozone destruction developed 20 years ago2 (see graphic). If the rate is substantially lower than previously thought, then it would not be possible to create enough aggressive chlorine radicals to explain the observed ozone losses at high latitudes, says Rex. The extent of the discrepancy became apparent only when he incorporated the new photolysis rate into a chemical model of ozone depletion. The result was a shock: at least 60% of ozone destruction at the poles seems to be due to an unknown mechanism, Rex told a meeting of stratosphere researchers in Bremen, Germany, last week.
Other groups have yet to confirm the new photolysis rate, but the conundrum is already causing much debate and uncertainty in the ozone research community. “Our understanding of chloride chemistry has really been blown apart,” says John Crowley, an ozone researcher at the Max Planck Institute of Chemistry in Mainz, Germany.
“Until recently everything looked like it fitted nicely,” agrees Neil Harris, an atmosphere scientist who heads the European Ozone Research Coordinating Unit at the University of Cambridge, UK. “Now suddenly it's like a plank has been pulled out of a bridge.”
The measurements at the Jet Propulsion Laboratory were overseen by Stanley Sander, a chemist who chairs a NASA panel for data evaluation. Every couple of years, the panel recommends chemical kinetics and photochemical data for use in atmosphere studies. Until the revised photolysis rate has been evaluated, which won't be before the end of next year, “modellers must make up their minds about what to do,” says Sander. One of the problems with checking the data is that the absorption spectra of chloride compounds are technically challenging to determine. Sander's group used a new technique to synthesize and purify Cl2O2. To avoid impurities and exclude secondary reactions, the team trapped the molecule at low temperatures, then slowly warmed it up.
“Reactions in experimental chambers are one thing — the free atmosphere is something else,” says Joe Farman, one of the scientists who first quantified the ozone hole over Antarctica3. “There's no doubt that ozone disappears at up to 3% a day — whether or not we completely understand the chemistry.” But he adds that insufficient control of substances such as halon 1301, used as a flame suppressor, and HCFC22, a refrigerant, is a bigger threat to the success of the Montreal Protocol than are models that don't match the observed losses.

Hot topic

Meanwhile, atmosphere researchers have started to think about how to reconcile observations of ozone depletion with the new chemical models. Several thermal reactions, or combinations of reactions, could fill the gap. Sander's group has started to study possible candidates one by one — but so far without success.
Rex thinks that a chemical pathway involving a Cl2O2 isomer — a molecule with the same atoms but a different structure — might be at play. But even if the basic chemical model of ozone destruction is upheld, the temperature dependency of key reactions in the process could be very different — or even opposite — from thought. This could have dramatic consequences for the understanding of links between climate change and ozone loss, Rex says.
The new measurements raise “intriguing questions”, but don't compromise the Montreal Protocol as such, says John Pyle, an atmosphere researcher at the University of Cambridge. “We're starting to see the benefits of the protocol, but we need to keep the pressure on.” He says that he finds it “extremely hard to believe” that an unknown mechanism accounts for the bulk of observed ozone losses.
Nothing currently suggests that the role of CFCs must be called into question, Rex stresses. “Overwhelming evidence still suggests that anthropogenic emissions of CFCs and halons are the reason for the ozone loss. But we would be on much firmer ground if we could write down the correct chemical reactions.” 
  • References

    1. Pope, F. D., Hansen, J. C., Bayes, K. D., Friedl, R. R. & Sander, S. P. J. Phys. Chem. A 111, 4322–4332 (2007). | Article | PubMed | ISI | ChemPort |
    2. Molina, L. T. & Molina, M. J. J. Phys. Chem. 91, 433–436 (1987). | Article | ISI | ChemPort |
    3. Farman, J. C., Gardiner, B. G. & Shanklin, J. D. Nature 315, 207–210 (1985). | Article | ISI | ChemPort |

The CFC Ban: Global Warming's Pilot Episode

Although it has been only a little over twenty years since the Montreal Protocol, which effectively created a global ban on chlorofluorocarbons (CFCs), the interesting history of the ozone hole has slipped under the radar, largely eclipsed by the much greater story of the anthropogenic global warming fraud. It's interesting to revisit the CFC/ozone depletion scam and note the striking similarities to the current campaign against CO2.

Chlorofluorocarbons were primarily used as refrigerants, propellants, and in fire control systems. They were uniquely well-suited to these applications. CFCs are non-toxic, chemically inert, non-corrosive, non-flammable and roughly four times heavier than air. Their physical characteristics makes them ideal refrigerants. Because they are so chemically inert, non-toxic, and non-flammable, they are excellent aerosol propellants. They are inexpensive to produce and easy and safe to handle. CFCs made modern refrigeration and air conditioning affordable and widely available.

Back in the early '70s, chemists at the University of California began studying CFCs in the atmosphere. They theorized that eventually, CFCs could migrate to the upper atmosphere. After fifty to a hundred years, they could be broken down by UV radiation, releasing a reactive chlorine atom which could catalyze the degradation of ozone (O3). It is significant to note that this was not proven, but was based on other work that showed the potential of nitric oxide (NO) to catalyze ozone. It was theory only, and it was hotly disputed by scientists working for CFC manufacturers at the time. In reality, it remains theory to this day. Note: To date, the concept of man-made CO2 emissions causing global warming remains theory only. There exists no empirical evidence to support the theory.

Then, in 1985, the journal Nature (sound familiar?) published an article by some British researchers who reported observing a greater degree of thinning of the Antarctic ozone layer than expected. Thus was born the "ozone hole." To appreciate this, one must understand a little about atmospheric ozone. Ozone is a very unstable form of oxygen that consists of three oxygen atoms per molecule. When atmospheric oxygen (O2) reacts with UV radiation, two unstable atoms of highly reactive oxygen (O) are produced. These will rapidly react to form either stable O2 or unstable O3. Ozone is constantly being created and destroyed in the upper atmosphere. Its creation is dependent upon sunlight and high-energy UV radiation. Ozone "holes" over Arctic and Antarctic regions have been well-known by atmospheric scientists for many decades. These areas of stratospheric thinning of O3 concentrations are associated with winter (i.e., no sunlight). Upper atmospheric ozone is important, as it absorbs UV-B radiation (280-320 nm). Strangely, the most significant thinning of the ozone layer has been observed over the Antarctic. Most CFC use has been in the northern hemisphere.

So two theories came together. Man-made CFCs could theoretically hasten destruction of stratospheric ozone, and British researchers observed greater thinning of Antarctic ozone than they "expected" (although at the time, this phenomenon was poorly understood, and no one knew what to "expect"). Almost immediately, human health threats erupted, most notably the threat of an increased incidence of malignant melanoma. This is interesting, as melanoma is not influenced by UV-B radiation, but rather UV-A radiation (which is not blocked by ozone). In the early '90s, the EPA estimated an additional 200,000 cancer deaths by 2050. But even before this, the scam had found a voice and a message. Mankind was sowing the seeds of its own destruction. Does this sound familiar?

The other significant coincidence that happened about this same time was that DuPont, a major CFC manufacturer, was poised to lose its patent on one of the most widely-used CFCs. Three Canadian investors who owned 25% of the company led the campaign to ban CFCs. DuPont initially fought the CFC phase out, but the company finally acquiesced when it had secured a patent on a CFC substitute. After all, billions of dollars were at stake.

The media never seemed to report the real economic impact of the CFC ban. Replacing CFCs was not at all easy. There really are no suitable, safe, and affordable replacements for Halon fire control systems. Most propellants were not too difficult to replace (although many are flammable). One notable exception is the CFC propellant used in metered dose inhalers of asthma medication. CFCs were ideal for this application because they are both chemically and biologically inert. Eventually, the pharmaceutical industry found a solution: hydrofluoroalkanes (HFA). Of course, this new delivery method meant that previously inexpensive generic drugs (e.g., albuterol) suddenly became expensive proprietary drugs. The CFC ban effectively tripled the cost of managing asthma. 

From the time the "Freon phase out" began, virtually hundreds of millions of refrigeration systems worldwide had to be replaced. This included automobiles, homes, businesses, and food and medical refrigerators. The systems still functioned, but they could not be economically recharged with CFCs (does this sound familiar?). This enormous cost continues to be silently passed on to consumers. It is important to recognize that the alternatives to CFCs are many orders of magnitude more expensive than CFCs themselves. This is roughly analogous to comparing the cost per kwh of electricity produced by coal versus solar or wind.

In the end, a global ban on CFCs was enacted based on a theory that continues to be challenged to this day. Chemists remain uncertain of the rate and extent of ozone depletion due to chlorine. In fact, the exact role of atmospheric CFCs remains uncertain. It appears that the primary catalyst of ozone depletion is atmospheric chlorine, and the most atmospheric chlorine by far is out-gassed from the oceans or emitted by volcanoes. Mankind's contribution is miniscule (does this sound familiar?). Further, natural processes have by far the greatest influence on the ozone layer (e.g., solar influence).

The CFC ban was a perfect pilot for the anthropogenic global warming fraud. It established all the characters: the eco-left NGOs, the environmental "scientists" (both real and self-proclaimed), and big industry poised to make huge profits and political control over human choices and behavior. It had buy-ins by governments all over the planet. It was based on an unproven (and probably unprovable) hypothesis. Many industries stood to gain at the expense of consumers. To this day, research continues to be funded to study CFCs in the atmosphere. Most significantly, the "ozone hole" hasn't changed appreciably. It remains if we ever really knew what "stable" was.

The CFC ban empowered and emboldened the eco-left. It paved the way for their next big scam. The environmentalists scored a big win when they finally banned DDT and doomed millions to a bleak death. Their subsequent eco-scares were not so successful. They were never able to affect global action in their belief in zero population growth. Widespread starvation and scarcity of resources has not happened. Pesticides and herbicides have proven not to be deadly to children. Acid rain has not resulted in widespread deforestation. High power transmission lines do not cause cancer. The use of chlorine produces more safe, potable water than any other intervention. The CFC ban gave them a "win," and it was based on some of the most specious, tenuous science one can imagine. But it proved a point: Proven science need not trump environmental ideology.

Their next target -- perhaps the ideal target of CO2 -- was in their sights. Noise about global warming started in the late '80s, but it didn't really get much traction until the mid- to late '90s...right after the CFC ban was a done deal.

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