CFC Destruction of Ozone - Major Cause of Recent Global Warming!
Robert A. Ashworth
The animation illustrates how one chlorine atom in the stratosphere
can destroy up to 100,000 ozone molecules. Graphic credit goes to
University of Alaska
There has been a lot of discussion about global warming. Some say anthropogenic carbon dioxide (CO2) emissions caused the earth to warm. Others say there is no abnormality at all, that it is just natural warming. As you will see from the data presented and analyzed, a greater than normal warming did occur in recent times but no measurements confirm an increase in CO2, whether anthropogenic or natural, had any effect on global temperatures. There is however, strong evidence that anthropogenic emissions of chlorofluorocarbons (CFCs) were the major cause of the recent abnormal warming.
CFCs have created both unnatural atmospheric cooling and warming based on these facts:
Many scientists do not agree with the CO2 global warming models developed by the Intergovernmental Panel on Climate Change (IPCC). For instance, T.M.L. Wigley 1, a senior scientist at the U.S. National Center for Atmospheric Research, calculated the "saved" warming that would accrue if every nation met its Kyoto Protocol obligations (U.S. reduction of 43%). By 2050, the earth’s temperature would reduce by 0.07 oC - a change so small it could not be reliably measured. In contrast to Wigley's projections, the IPCC has developed models 2 that predict the average surface temperature of the earth relative to 1980-1990, will increase by 2 to 11.5°F (1.1 to 6.4°C) by the end of the 21st century due to increased CO2 concentrations in the atmosphere. They project temperature change as functions of growth rates in atmospheric carbon dioxide. Those projections are shown in Figure 1.
Figure 1. IPCC projections of global warming.
What is so disturbing is that measured temperature points added to the IPCC graph do not show the temperature has increased. Further, temperatures for over 1200 years (see Figure 2) show absolutely no correlation with CO2 concentration in the atmosphere. Note that the 210 to 312 ppmv scale is in larger increments than the upper 312 to 378 ppmv scale, visually making the CO2 increase look greater than it actually was. The temperature is jumping around and not following CO2 concentrations at all. The IPCC models are clearly flawed. One must wonder whether the IPCC used any actual temperature measurements or historic CO2 concentrations relative to global temperature, when it developed its models. After developing the models, it does not look like they checked their predictions against real measurements. If so, CO2 causing global warming would have been negated by now.
Figure 2. CO2 concentration and temperature change with time from 800 to 2006 AD 3.
As shown in Figure 2, over the time from 850 until 1650, the CO2 concentration was relatively the same (~230 ppmv) but the earth's temperature varied from +0.6 to -0.2 o C. The CO2 concentration was 375 ppmv in 2006 and there was still no correlation of temperature with CO2 concentration
Some say historically, that increased CO2 levels in the atmosphere have created periods of global warming. They cite the Vostok, Antarctica ice core data 4, as proof of this. The truth here is that whoever came up with this analysis got the cause and effect reversed. The data show that global warming always comes first (refer back to Figure 2). After a temperature spike from by the sun, the oceans start to warm and liberate more CO2 because of the reduced solubility of CO2 in seawater at higher temperatures. After a spike, there is a lag of some 800+ years until CO2 concentration in the atmosphere starts to increase.
Data that is more recent, further confirm that atmospheric CO2 concentrations have no effect on global temperature, see Figure 3. While CO2 levels increased some 20 ppmv over the past 10 years, global temperatures did not increase they fell. For instance, the earth's temperature from January 2007 to January 2008 dropped by almost 0.6 oC.
Figure 3. Earth temperature and CO2 concentration 1998-2008.
The temperatures shown in the graph 5 are from the National Aeronautics and Space Administration's (NASA) Microwave Sounding Unit (MSU) and the United Kingdom's (UK) Hadley Climate Research Unit. The Mauna Loa Observatory in Hawaii measured concentrations of CO2 in the atmosphere over this same period. Here again, actual data completely refutes IPCC modeling predictions. Even further, human emissions account for only some three percent (3%) of the total CO2 in atmosphere 6 or some 12 ppmv of the 385 ppmv seen in 2008. Therefore, if anthropogenic emissions of CO2 had been banished completely at the start of 2008 the CO2 in the atmosphere would have dropped only back to the level we had in mid 2002. It was also warmer in 2002 than it was in 2007. Although one would prefer not to refute another's work, the more you study CO2 causing global warming, the more ludicrous it becomes.
Besides the carbon dioxide increase in the atmosphere, atmospheric concentrations of methane have increased 2.5 times from pre-industrial time (approximately 700 ppbv) to 1,745 ppbv in 1998 7. In 1966, the methane concentration was around 1400 ppbv. In 2000, methane concentrations leveled off at 1755 ppbv and currently appear to be slowly dropping. This is during the same time span when stratospheric CFC concentrations leveled off and started to drop slowly. Where is this methane coming from? Much of it could be from the melting of permafrost. A recent study 8 showed that permafrost melting in North Siberia is releasing methane sequestered there since the Pleistocene era (10,000 to one million years ago) from the surface of thawing lakes. Further, methane is being emitted at a rate much greater than previously thought. The methane being released was estimated to be some 100 times the rate of carbon dioxide released from the burning of fossil fuels. Methane (CH4) slowly converts to CO2 in the atmosphere. If the researchers from Florida, Alaska and Russia are correct, it appears that most of the recent CO2 increase has come from the melting of permafrost.
Ozone Loss Effect
In 1994, ozone in the lower stratosphere in Antarctica had dropped to less than one-third of its normal level. Although not as severe, ozone concentration north of the Arctic Circle sank to 45% of normal in the winter of 1996.
The legendary hypotheses 9 of Paul Crutzen, Sherwood Rowland, and Mario Molina led to CFCs being banned because they were destroying stratospheric ozone. Although it unleashed a storm of criticism and controversy at the time they did their work, they were vindicated by receipt of the 1995 Nobel Prize in Chemistry. In 1978, the USA banned the use of CFCs in hair sprays and other aerosols. In 1987, the governments of the world through the United Nations Environment Programme (UNEP), agreed to limit the production and release of a variety of CFCs. The protocol to accomplish this was put forward at a meeting in Montreal, Canada and has since become known as the Montreal Protocol. Since the original protocol, its provisions were amended in mid-1998; the amendments were then ratified or accepted by 120 and 78 countries, respectively. CFCs will be produced in China and other developing countries until 2010. However, in July 2007, China shut down five of its six remaining CFC production plants ahead of schedule and now is only producing 550 metric tons per year.
It is well known that warming of the stratosphere is caused by ozone absorbing ultraviolet radiation. Since ozone keeps the stratosphere warm, using straightforward logic, loss of ozone would cause the stratosphere to cool. When ozone is lost, more UV light passes through the stratosphere to hit earth. The effect is clearly shown (Figure 4) by temperature versus ozone concentration in Dobson Units (DU). NASA 10 generated the graph below.
Figure 4. Ozone concentration versus stratospheric temperature.
Except for the periods of two large volcanic eruptions, temperature and ozone concentration rise and fall together. From 1997 to 2001, the temperature of the stratosphere averaged a 1 oC change for every 6.45 DU of increase or decrease in stratospheric ozone concentration. Over the Polar Regions, the primal cause for colder than normal temperatures is loss of ozone. During winter, the air temperature drops and clouds of ice crystals, with mixtures of hydrochloric, sulfuric and nitric acids, form in the stratosphere. These ice crystals provide a surface for chemical reactions that change chlorine compounds that do not react with ozone (e.g. hydrogen chloride) into more active forms that destroy ozone, such as:
HCl + ClONO2 -> Cl2 + HNO3 and CL2 + UV -> 2 Cl -
In addition, the very cold air creates vortices of fast-moving air. These vortices effectively insulate the Polar Regions from the rest of the atmosphere. They sit there, are very stable, and keep the outside higher-ozone air from coming in. Most stratospheric ozone is created in the tropics because of the greater intensity of solar radiation that creates ozone. Stratospheric air currents, from the tropics, then transport ozone to the Arctic and Antarctica. However, the strong and stable vortices hinder the migration of ozone to the poles and more UV light passes through to hit earth. That is why the Polar Regions have warmed more that the rest of the earth.
Since the late sixties, the loss of ozone has caused the stratosphere to cool, see Figure 5. The exceptions to cooling caused by ozone destruction occurred at the times of the major eruptions of El Chichon, and Mt. Pinatubo volcanoes. The Agung volcanic eruption that occurred before the time interval analyzed also warmed the stratosphere. In 1980, Mt. St. Helens erupted but it had a much smaller effect than El Chichon and Mt. Pinatubo. In 1998, the stratosphere was 1.37 oC cooler than it was in 1966. This span of time was chosen to negate the solar irradiance cycle and the volcanic eruption effects. The data suggests that the cooling over this time span appears to be mostly due to loss of ozone.
Figure 5. Global lower stratospheric anomalies from 1958 to 2008 11.
The temperature changes before 1966 are most likely the result of change in the rate of solar energy that hits earth and maybe some volcanic activity. However, after CFC refrigerants and aerosols started to be produced and released to the atmosphere, the stratosphere started to cool. As the lower stratosphere and upper troposphere cooled, the troposphere and earth from 1966 to 1998 warmed by 0.48 oC see Figure 6. The mean used for this graph to set a zero temperature is different from Figure 5 but since only temperature change is being considered, the line depicting the zero point is irrelevant.
Figure 6. Near earth surface temperature global change with time 12.
In the Arctic, surface temperatures increased 2 ˝ times the average global increase (1.2 oC vs. 0.48 oC) from 1966 to 1998, see Figure 7. This appears to be caused by less ozone in the stratosphere in polar climes where ozone destruction is exacerbated.
Figure 7. Observed Arctic temperature change 13.
There is a cooling anomaly in Antarctica. Whereas, the Signey Island landmass in the northern part of Antarctica has warmed, south at Vostok, there has been a cooling effect. Although the cooling at Vostok needs to be analyzed in more detail, because of the large ozone hole in Antarctica, it seems likely that black body radiation from Vostok (some 11,400 feet above sea level) to outer space is most likely the cause, especially since this phenomenon occurred over the same time span that stratospheric ozone destruction took place. One would have to use reverse logic to explain the cooling effect at Vostok being caused by increased CO2 in the atmosphere.
The change in ozone depletion chemicals in the stratosphere versus time 14 plus future concentration projections is shown in Figure 8. CFC concentrations peaked in the late nineties and then started dropping slightly. The contribution of methyl bromide is split into anthropogenic (A) and natural (N) components and the natural ozone-depleting substance methyl chloride is included. The line at 2 ppb corresponds to the time when ozone depletion was first detected (1980). It also shows when major ozone recovery is anticipated (2050 to 2060). Although not shown, chloroform (CHCl3), dichloromethane (CH2Cl2), and a range of other chlorinated solvents contribute a further 0.1 ppb to the stratospheric chlorine.
Figure 8. Ozone depletion chemicals in the stratosphere.
CFC's and CCl4 are nearly inert in the troposphere and have lifetimes of 50-200+ years. The hydrogen-containing halocarbons like HCl are more reactive, and tend to be removed in the troposphere by reactions with [OH] radicals. However, this process is slow and some live long enough to reach the stratosphere. Total stratospheric organic chlorine is currently over 3 ppbv. Methyl Chloride (CH3Cl) is the only ozone-depleting chlorocarbon from a major natural source and makes up around 0.5 ppbv of the total. Organic bromides and iodides also destroy ozone.
It is different in the stratosphere; the major source of CFC decomposition there is photolysis 15, reaction with ultraviolet (UV) light radiation. Ultraviolet light has wavelengths in the 200-400 nm region. UV-A light is a low energy UV light with wavelengths between 320-400 nm. Only about 5% of the UV-A light is absorbed by ozone and most reaches the surface of the Earth. UV-B light is of moderate energy and has wavelengths between 290-320 nm. Ozone absorbs most of the UV-B light before it reaches the surface of the Earth. UV-C light is a high energy UV light with wavelengths in the range of 200-290 nm.
Both ozone and oxygen molecules absorb the UV-C light before it can reach the Earth's surface. Therefore, where there is low stratospheric ozone, more UV (A, B & C) light from the sun passes through the atmosphere to hit earth and heat it up.
The initial products from high energy UV-C light hitting a CFC molecule are a chlorine atom and an organic radical, considering CFC-11 (trichlorofluoromethane):
CCl3F + UV-C light = CCl2F + Cl
The free chlorine atom can then react with ozone to form ClO:
Cl + O3 -> ClO + O2
The ClO in turn will react with nascent oxygen (O) to release a chlorine atom; thus, a continuous destruction of ozone occurs because the chlorine atoms are not sequestered into stable compounds:
ClO + O -> Cl + O2
The CFC chlorine can take other reaction paths, but this is believed to be the predominant ozone destruction cycle. It has been estimated that one CFC molecule in the stratosphere will destroy 100,000 molecules of ozone over its natural lifetime there. Though the concentration of CFCs is only 3 ppbv, they have the ozone destruction effect of a concentration of 0.03% based on one reaction per ozone molecule.
Figure 9 shows a correlation of CFC concentration and average stratosphere and earth temperature plotted versus time. As shown by the arrows, in a logical sequence, CFC concentration started to drop first causing a reduction in stratospheric cooling and then a reduction in earth warming.
Figure 9. Stratospheric cooling, earth warming and CFC concentration.
When one sees like trends, it is a good indication that the trends are related to one another. Contrarily, when one looks at CO2 concentrations versus earth temperature there is no trend whatsoever that shows increased CO2 concentrations increase global temperature. The only observable trend between the two is that a global spike from the sun creates a higher temperature on earth and some 800 years or so later the CO2 concentrations in the atmosphere start to increase.
Large solar heating-cooling cycle variations occur every 80,000 to 110,000 years, but the sun's thermostat also regularly increases and decreases in shorter term cooling-warming cycles (approximately 11 years) 16, see Figure 10. For the mass and energy balances completed, to eliminate the short-term solar irradiance warming-cooling cycle effect on global warming, the period from 1966 to 1998 was chosen. At these two points in time, the solar irradiance hitting the earth was approximately the same (1368.8 W/m2).
According to NASA, the lower stratosphere and upper troposphere, both of which have cooled together 17, extends from 8 to 19 km above the surface of the earth with the lower troposphere being in the 0 to 8 km elevation zone. Knowing how much the lower stratosphere-upper troposphere cooled and how much the lower troposphere-earth warmed, mass and energy balances could be made to determine how much more radiant energy hit the earth in 1998 compared to 1966 due to the destruction of ozone.
Figure 10. Solar irradiance cycle effect on earth.
Table 1 shows the mass and energy balances completed around the lower stratosphere/upper troposphere (8-19 km above sea level) zone, 1966 versus 1998 based on measured atmospheric temperatures that showed these zones had cooled 1.37 oC over this time span. The mass and energy balance in Table 2 shows the effect of the additional energy being absorbed by the troposphere/earth (surface to 8 km above sea level) in 1998 compared to 1966. It is similar to this. Say you have one million pounds of water. You measure the temperature of the water, and then you add one million Btus of energy to it and measure the temperature again to find it has raised 1 oF. The additional UV radiation passing through the upper atmosphere is sufficient to heat the lower troposphere and the top 8-3/4 inches of the earth by 0.48 oC. The temperature of the lower troposphere and 8-3/4" of earth (land and water) in 1966 had an average heat content of 9.7755 x 10 20 Btu and in 1998; it had a heat content of 9.7924 x 10 20 Btu. The added instantaneous UV energy that hit the earth in 1998 was 1.6855 x 1018 Btu. The added energy hitting the earth was used to first heat the troposphere and the remaining energy was then applied to heat land and water. To make the energy balance, 8-3/4" of earth/water needed to be heated.
TABLE 1. UV-B LIGHT NOT ABSORBED IN UPPER TROPOSPHERE/LOWER STRATOSPHERE
TABLE 2. HEAT ABSORBED IN LOWER TROPOSPHERE AND EARTH SURFACE
Ozone Signature Present but No Greenhouse Signature
There are several possible causes of global warming, and they each warm the atmosphere at different latitudes and altitudes, that is, each cause will produce a distinct pattern of hot spots in the atmosphere, or “signature”. The greenhouse signature is very distinct from the others; warming due to a greenhouse effect would cause most warming in the tropics at about 10 km up in the atmosphere 18.
If the IPCC is right about a greenhouse effect, do actual temperature measurements show a hot spot like they predict from their signature modeling efforts? The answer is no! Therefore, one cannot in good conscience say CO2 is causing global warming through a greenhouse effect that is not there. It exists, but there is no signature for its existence?
Temperature in the atmosphere has been measured for decades using radiosondes (a technique where weather balloons with thermometers radio back the temperature as the balloon ascends through the atmosphere). Actual measured temperatures (Hadley Centre radiosonde observations) for 2006-2007 are shown in Figure 11. The measurements show mostly warming in the troposphere and on earth with cooling in the stratosphere
Figure 11. Observed signature from actual measurements 19.
The axes for the observed temperatures are as per the signature diagrams developed by the IPCC shown in Figure 12. However, the horizontal axis only goes from 75 degrees north to 75 degrees south, there is no data around 60 degrees south, the vertical axis only goes up to 24 km and there was no data above 20 km for the equator area. The vertical axis shows the height in the atmosphere in kilometers (km) and the atmospheric pressure in hectopascals (hpa).
The six theoretical computer model signatures developed (Figures 12 a through f) by the IPCC 20, which is the most authoritative document for those who believe carbon emissions have caused global warming. In each diagram, the horizontal axis is the latitude, from the North Pole through the equator to the South Pole. The colored regions on each diagram, shows where the temperature changes occur for each possible cause. Here also, the vertical axis shows the height in the atmosphere in kilometers (km) and the atmospheric pressure in hectopascals (hpa).
Figure 12. IPCC projected climate change signatures.
Figure 12a is the signature developed for increased solar irradiation. If this signature were present, the warming would be moderate through most of the stratosphere and troposphere. This effect is not seen.
Figure 12b is the signature of a large volcanic eruption producing huge clouds of ash and fumes. If this signature were present, there would be moderate warming above 14 km, and moderate cooling below that. The opposite of this effect is seen, cooling in the stratosphere and warming in the troposphere.
Figure 12c is a signature of an increase in greenhouse gases, including carbon dioxide. If this signature were present, warming would be concentrated in a distinct “hot spot” about 8 to 12 km up over the tropics, with less warming further away, turning to cooling above 18 km. No "hot spot" seen.
Figure 12d is a signature of increased ozone depletion (both tropospheric and stratospheric). The ozone signature shows moderate warming below 12 km and moderate cooling above 12 km. This effect is seen and was probably more pronounced in 1998 when it was hotter on the earth than it was in 2007.
Figure 12e is a signature of increased industrial pollution, specifically direct sulfate aerosols. If this signature were present, there would be moderate cooling below 14 km mainly in the northern hemisphere and moderate warming above 14 km over the tropics. A little bit of this could be occurring around the equator and in the southern hemisphere.
Figure 12f is the signature that was expected by the IPCC, developed by combining the five signatures. The combination was made in the proportions the IPCC believed those causes contributed to global warming. The distinct "hot spot" at 8 to 12 km high over the tropics due to increased greenhouse warming dominates the theoretical combined signature. Actual measurements do not show this effect.
There is clearly no "hot spot" as the IPCC predicted; the "greenhouse signature" is absent, which means greenhouse gases did not cause the earth to warm. After the greenhouse signature was found to be missing, alarmists objected by saying the readings of the radiosonde thermometers might not be accurate and maybe the hotspot is there but went undetected. The uncertainties in temperature measurement from one radiosonde is large enough to miss the hotspot; however, hundreds of radiosondes have given the same answer, so statistically it is not possible that they collectively failed to notice the hotspot.
The signature that is the closest to the actual warming signature is the "ozone depletion signature"; refer back to Figure 12d where it showed moderate warming below 12 km and moderate cooling above 12 km. This effect dominates in the northern hemisphere from 20o to 75oN north. It is not an exact fit for the observed signature all over the globe but clearly appears to play the dominant role. The ozone signature also shows greater warming in the North Polar Region like is currently seen. In the IPCC ozone signature presented, there was no projection for the South Polar Region. Effects like industrial pollution and other currently unknown effects could be playing minor roles based on the IPCC models.
Many factors can influence the earth's temperature. However, from a scientific analysis, there is not a greenhouse signature in the atmosphere as implied by the IPCC. The non-effect of CO2 is also clearly shown, by an earth temperature drop of almost 0.6 oC from January 2007 to January 2008. It should be obvious to everyone who has analyzed climate change that climate-driving forces, other than CO2, control the temperature.
As this paper addresses, chlorofluorocarbon destruction of stratospheric ozone can be correlated nicely with both the cooling and warming temperature anomalies seen over the time span from 1966 to 1998 and the ozone signature for global warming is the closest of the five signature impacts developed by the IPCC. Further, one can account for most, if not all, of the 0.48oC rise in earth's temperature from 1966 to 1998 with the additional UV light that hit the earth due to ozone destruction in the upper atmosphere. Further, the "ozone depletion signature" developed by the IPCC for the atmosphere is seen but not the "greenhouse signature".
Ozone destruction has also indirectly created an increase in CO2 concentrations due to the melting of the permafrost in Siberia that has warmed two and one-half (2˝) times more than the average earth temperature has risen. The higher temperatures started melting the permafrost, and this in turn created a significant release of methane. Methane slowly reacts with oxygen to convert to CO2 in the atmosphere.
Unless we remove the CFCs from the atmosphere, it appears that the whole earth will continue to be warmer than normal and higher concentrations of CO2 (from permafrost release of methane) will exist until the CFCs in the stratosphere slowly disappear naturally over the next 50-100 years. The exceptions that could alter this are large volcanic eruptions or weather modification techniques as proposed by physicist Freeman Dyson, wherein fine particulate, such as bauxite (Al2O3), is sprayed into the stratosphere to simulate a volcanic eruption, which would absorb more UV light in the stratosphere and cool the earth as shown in the IPCC modeled signature for volcanic eruptions.
China and other developing countries are to phase out CFC production in 2010. Some CFC production plants have been shutdown ahead of schedule in these developing countries, which is very beneficial. However, it would not be that difficult to remove CFCs from the atmosphere to bring earth's temperature back to normal much quicker. Although the atmosphere is intricate in how it acts and reacts, CFCs appear to be the dominant cause of the greater than normal earth warming from 1966 to 1998, not CO2.
Einstein (21) once said, "The grand aim of all science is to cover the greatest number of empirical facts by logical deduction from the smallest possible number of hypotheses or axioms". One can do that here using CFC destruction of ozone to explain the observed recent earth temperature anomalies.
The United States Congress will be considering a $1.2 trillion carbon tax this year that, if implemented, would make the recent increase in the cost of gasoline look pale in comparison to the price it will be after such a tax is imposed. Taxing carbon makes absolutely no sense and will dramatically hurt the economy of every country that implements it - all for no useful reason! This paper is a direct challenge to the IPCC; its models are way off base. When one develops a model, actual data needs to be observed to confirm or refute the model that one develops. It does not look like the IPCC knows this.
I would like to thank Christopher Monckton and David Evans for their support and suggestions. Most of all I would like to pay tribute to three gentlemen; Paul Crutzen, Sherwood Rowland, and Mario Molina, who saved this earth through their work on the CFC effect on the environment. If they had not worked to stop CFC production, what we are seeing now with global warming would be nothing compared to how bad it would have been without their efforts to stop its production. Their work was not only important from the standpoint of reducing global warming, but also in reducing the occurrence in skin cancer.
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