In creating this blog I found that all my posts have come out in the reverse order to which I intended them to be read. To save you the reader the hassle of having to plough back through my previous posts I have decided to create a contents page here with links to each section in the order they were originally intended. Of course you are free to view them in any order you choose. So just click on a link and enjoy learning.
Section 1: Introduction to me, my motivation and my blog:
1. Introduction
Section 2: Background information on CO2 and temperature:
2. Global warming from the Little Ice Age
3. Global warming since 1998
4. Global warming prior to the Little Ice Age
5. Global warming -CO2 - the facts
Section 3: Background information on the major groups and issues involved in the debate:
6. The three realities of climate change
7. The sceptics
8. Noble cause corruption in climate change
9. The Intergovernmental Panel for Climate Change (IPCC)
10. The IPCC and the Hockey stick graph
11. Chartmanship
12. The IPCC's 4th Assessment Report
13. The IPCC's 2500 scientists and the consensus of scientific opinion
14. The 31,072 scientists who oppose the IPCC's position
15. US Senator James Inhofe's 650 dissenting scientists
16. Climate Alarmism and Al Gore
17. Dr. James Hansen and alarmism
18. Professor Stephen Schnider and alarmism
19. Alarmism and the IPCC
20. Australian scientists and alarmism - Dr. David Karoly
21. Australian scientists and alarmism - Dr. Tim Flannery
22. Australian scientists and alarmism - Professor Matthew England
23. Australian scientists and alarmism - Professor Barry Brook
24. Australian scientists and alarmisim
25. Australian activists and alarmism
26. The media on climate change - part 1
27. The media on climate change - part 2
28. The media on climate change - part 3
29. The media on climate change - part 4
30. UK Met Office employs hindsight to claim prediction perfection.
31. Use of visual media as a propaganda tool
32. The reaction of some of the public to the media campaign on climate change
33. In the pay of "Big Oil" and other funding arrangements
34. Private beneficiaries of climate change
35. The 35 errors in "An Inconvenient Truth" - part 1
36. The 35 errors in "An Inconvenient Truth" - part 2
37. The 35 errors in “An Inconvenient Truth” – part 3
38. The 35 errors in “An Inconvenient Truth” – part 4
39. The 35 errors in “An Inconvenient Truth” – part 5
40. The 35 errors in “An Inconvenient Truth” – part 6
41. The 35 errors in “An Inconvenient Truth” – part 7
42. The 35 errors in “An Inconvenient Truth” – part 8
43. The 35 errors in “An Inconvenient Truth” – part 9
44. The 35 errors in “An Inconvenient Truth” – part 10
45. The 35 errors in “An Inconvenient Truth” – part 11
46. The 35 errors in “An Inconvenient Truth” – part 12
47. The 35 errors in "An Inconvenient Truth" - part 13
48. More errors by Al Gore
49. Do as I say, not as I do
50. The environmental activists hidden agendas
Section 4: The major issues:
51. Comic relief
52. The Polar Icecaps - part 1
53. The Polar Icecaps - part 2
54. The Polar Icecaps - part 3
55. The Polar Icecaps - part 4
56. The Polar Bears
57. Permafrost
58. Rising seas - part 1
59. Rising seas - part 2
60. Rising seas - part 3
61. Acid seas and coral reefs - part 1
62. Acid seas and coral reefs - part 2
63. Acid seas and coral reefs - part 3
64. Hurricanes and cyclones
65. Drought and the Murray Darling Basin
66. Temperature and the natural cycles
67. The Pacific Decadal Oscillation (PDO)
68. The Atlantic Multi-Decadal Oscillation (AMO)
69. Air and ocean temperatures
70. Transition to Solar cycle 24
71. Cosmic rays
72. Urban Heat Island effect
73. Mosquito borne diseases
Section 5: The proposed cures for climate change
74. The alternate energy systems
75. Wind power - part 1
76. Wind power - part 2
77. Wind power - part 3
78. Solar power - part 1
79. Solar power - part 2
80. Solar power - part 3
81. Other renewable sources of power
82. Nuclear - part 1
83. Nuclear - part 2
84. Nuclear - part 3
85. Other "Green" initiatives - biofuels
86. Other "Green" initiatives - hybrid /electric cars
87. Other "Green" initiatives - Compact Florescent Lights (CFL's) - part 1
88. Other "Green" initiatives - CFL's - part 2
89. Other "Green" initiatives - CFL's - part 3
90. Other "Green" initiatives - CFL's - part 4
91. The list of all things caused by global warming
92. Conclusion
Section 6: Conclusion of Sections 1 to 5
Section 7: Updates
93. More Hockey Stick Graph Controversy
94. Antarctic Not Melting During Summer
95. Cosmic Rays Hit Space Age High
96. Quiz Time
97. Alarmists Deliberately Target Children
98. Alarmists Deliberately Target Children - Part 2
99. Dr. James Hansen's Failed Prediction
100. Yet More Political Support For Alarmism
101. Dr. Richard Lindzen Discusses Climate Change
102. The Climate Research Unit Email Scandal
103. The Global Warming Swindle Movie
104. More Informational Videos
105. Climategate (The C.R.U. EMail Scandal) Update
106. Professor Bob Carter on CO2 and Climate Change
107. The Debate
108. Report from Copenhagen
109. Hiding the Decline - Part 1
110. Hiding the Decline - Part 2
111. Hiding the Decline - Part 3
112. Hiding the Decline - Part 4
113. Hiding the Decline - Part 5
114. Hiding the Decline - Part 6
115. Australian Bureau of Meteorology (BoM) dismisses what it should be revealing
116. Cloud Mystery Video Series
117. Those Who Control The Information Try To Control The Debate.
118. Glaciergate And The TERI Link
119. No Peer Review Required At IPCC
120. The CRU Was Not Alone In Manipulating Data
121. How GISTEMP Produce Their Fudged Data.
122. Dr. Richard Lindzen - The Earth Is Never In Equilibrium
123. Climategate Enquiries And The Tom Sawyer Effect
124. Would You Trust Truth Fudgers?
125. When Scientists Go Bad
126. Tuvalu - The Defiant Island
127. Update On Wind Power Generation
128. Anthony Watts Discusses His Surface Stations Project
129. More Evidence Of Enhanced Global Temperature Data
130. Dr. Roy Spencer's Global Warming For Dummies
131. "Even if we have to redefine what the peer-reviewed literature is".
132. IPCC Continues To Fail In Its Bid For Accuracy
133. Failing To Convince, Climate Activists Threaten Instead
134. Stinks Of Desperation By The Alarmists.
135. A Very Important Letter
136. New Peer Reviewed Study Rebuts Steig et al Study on Antarctic
137. New Peer Review Study Rebuts Schmidt Paper on Surface Temperature Measurements
138. New Peer Reviewed Study Shows Just How Bad Climate Models Are
139. New Peer Reviewed Paper Shows “Absence Of Correlation Between Temperature Changes … And CO2″
140. Is The Warming Still Too Large To Be Explained By Solar?
141. CERN CLOUD Experiment - Preliminary Results
142. Global Warming Panic Explained
143. Two Important Interviews In The Carbon Dioxide Tax Debate
144. Sea Levels Don't Respond To Alarmism
145. Geoengineering - Not Quite The Fix They Thought It Was
146. Latest News From CERN CLOUD Experiment
147. New Study Links Cosmic Rays To Aerosols/Cloud Formation Via Solar Magnetic Activity Modulation
148. New Study Admits “Global Surface Temperatures Did Not Rise Between 1998 and 2008″
149. Dr Judith Curry - An explanation(?) for lack of warming since 1998
150. Dr. Roy Spencer's Video
151. Climategate Vs Fakegate
152. CO2 Causes Temperature Change or Vice Versa?
153. Polar Bear Numbers Increasing
154. Cosmic Rays And Clouds Influence Climate
155. New Peer Reviewed Paper Claims Global Warming Not Human Influenced
156. Reporting Impending Climate Doom
157. Part 2 of Professor Don Easterbrook's Concerns About The "Shakun et al Paper"
158. Paper Unifying Cosmic Ray Interaction
159. Another Paper Supports Svensmark's Cosmic Ray Theory
160.
Sunday, April 14, 2013
Another Paper Supports Svensmark's Cosmic Ray Theory
In recent weeks there has been even further developments in support of Svensmark's Cosmic Ray Theory of cosmoclimatology. Via The Hockey Schtick is this article:
A paper published today in the Journal of Atmospheric and Solar-Terrestrial Physics finds "strong evidence" of a link between thunderstorm and solar activity in Brazil from 1951-2009. According to the authors, thunderstorm "behavior with respect to the 11-year solar cycle suggest a global mechanism probably related to a solar magnetic shielding effect acting on galactic cosmic rays as an explanation for the relationship of thunderstorm and solar activity," which would corroborate Svensmark's theory of cosmoclimatology.
A paper published today in the Journal of Atmospheric and Solar-Terrestrial Physics finds "strong evidence" of a link between thunderstorm and solar activity in Brazil from 1951-2009. According to the authors, thunderstorm "behavior with respect to the 11-year solar cycle suggest a global mechanism probably related to a solar magnetic shielding effect acting on galactic cosmic rays as an explanation for the relationship of thunderstorm and solar activity," which would corroborate Svensmark's theory of cosmoclimatology.
The relationship between thunderstorm and solar activity for Brazil from 1951 to 2009
- a Camilo Castelo Branco University (Unicastelo), São Jose dos Campos, Sao Paulo, 12247-004, Brazil
- b ELAT/CCST, National Institute of Space Research (INPE), São Jose dos Campos, Sao Paulo, 12227-010, Brazil
Highlights
- •
- First results on the relationship between solar and thunderstorm activity in Brazil.
- •
- Strong evidence of anti-phase correlation between solar and thunderstorm activity in Brazil.
- •
- New statistical method for evaluating correlation between solar and thunderstorm activity.
Abstract
The goal of this article is to investigate the influence of solar
activity on thunderstorm activity in Brazil. For this purpose, thunder
day data from seven cities in Brazil from 1951 to 2009 are analyzed with
the wavelet method for the first time. To identify the 11-year solar
cycle in thunder day data, a new quantity is defined. It is named TD1
and represents the power in 1-year in a wavelet spectrum of monthly
thunder day data. The wavelet analysis of TD1 values shows more clear
the 11-year periodicity than when it is applied directly to annual
thunder day data, as it has been normally investigated in the
literature. The use of this new quantity is shown to enhance the
capability to identify the 11-year periodicity in thunderstorm data.
Wavelet analysis of TD1 indicates that six out seven cities investigated
exhibit periodicities near 11 years, three of them significant at a 1%
significance level (p < 0.01).
Furthermore, wavelet coherence analysis demonstrated that the 11-year
periodicity of TD1 and solar activity are correlated with an anti-phase
behavior, three of them (the same cities with periodicities with 1%
significance level) significant at a 5% significance level (p <
0.05). The results are compared with those obtained from the same data
set but using annual thunder day data. Finally, the results are compared
with previous results obtained for other regions and a discussion about
possible mechanisms to explain them is done. The
existence of periodicities around 11 years in six out of seven cities
and their anti-phase behavior with respect to 11-year solar cycle
suggest a global mechanism probably related to a solar magnetic
shielding effect acting on galactic cosmic rays as an explanation for
the relationship of thunderstorm and solar activity, although more
studies are necessary to clarify its physical origin.
Wednesday, October 31, 2012
Paper Unifying Cosmic Ray Interaction
In previous posts I have looked at the possibility of a link between Svensmark's Cosmic Ray theory as an alternate explanation of climate change, here, here, here, here, here, here and here.
Now to add to that series is this via WUWT:
Abstract
Numerous laboratory measurements have provided a sound physical basis for the cosmic-ray driven electron induced reaction (CRE) mechanism of halogen-containing molecules for the ozone hole. And observed spatial and time correlations between polar ozone loss or stratospheric cooling and cosmic rays have shown strong evidence of the CRE mechanism [Q.-B. Lu, Phys. Rep. 487, 141-167(2010)]. Chlorofluorocarbons (CFCs) were also long-known greenhouse gases but were thought to play only a minor role in climate change. However, recent observations have shown evidence of the saturation in greenhouse effect of non-CFC gases. A new evaluation has shown that halocarbons alone (mainly CFCs) could account for the rise of 0.5~0.6 °C in global surface temperature since 1950, leading to the striking conclusion that not CO2 but CFCs were the major culprit for global warming in the late half of the 20th century [Q.-B. Lu, J. Cosmology 8, 1846-1862(2010)].
Surprisingly, a recent paper [J.-W. Grooß and R. Müller, Atmos. Environ. 45, 3508-3514(2011)] has criticized these new findings by presenting “ACE-FTS satellite data”. Here, I show that there exist serious problems with such “ACE-FTS satellite data” because the satellite has essentially not covered the Antarctic vortex in the presented months (especially winter months during which most effective CRE reactions are expected) and that the criticisms do not agree with the scientific facts in the literature. Instead, real data from multiple satellites provide strong evidence of the CRE mechanism. So far, the CRE mechanism is the only one that reproduces and predicts 11-year cyclic variations of ozone loss in the Antarctic O3 hole and of resultant stratospheric cooling, and the CFC mechanism can well explain both recent global warming and cooling. These findings should improve our understandings of the ozone hole and global climate change.
Introduction
Both natural and human effects could alter the Earth’s climate and environment. The ozone hole and global temperature change have been two major scientific problems of global concern. There is long interest in studying the effects of cosmic rays (CRs)
on Earth’s ozone layer [1-17]. In the 1970s, the odd nitrogen (NOx) generated by solar particle events (SPEs) were proposed first by Crutzen et al. [1] for solar proton events and then by Thorne [3] for energetic electron precipitation events to cause transient O3 destruction in the upper stratosphere at altitudes above 30 km. And Ruderman et al. [2]
proposed that the 11-year solar cycle variation of the CR intensity may also result in a small modulation (2~3% above or below the mean value) of polar total O3. However, the sink of O3 by SPEs, often associated with very large solar flares, is expected to be most pronounced during solar maxima and opposite in phase to the O3 loss caused by CRs [3].
If these natural effects were appreciable, they would lead to an 11-year cyclic variation in any season (e.g., summer). However, observed O3 data show no considerable long-term correlation between total ozone in the summer polar stratosphere and solar activity / CRs These natural effects are very limited in the long-term total O3 variation. Direct measurements based on balloons and satellites have shown convincing evidence that the formation of the O3 hole is related to human-made chlorofluorocarbons (CFCs) such as CF2Cl2 (CFC-12) and CFCl3 (CFC-11).
In 1974, Molina and Rowland first proposed that CFCs are decomposed by photodissociation with UV sunlight (a process called photolysis). The liberated chlorine atoms contribute to the depletion of the O3 layer. This photolysis was originally predicted to happen in the upper tropical stratosphere at high altitudes of ~40 km. Then it came with a surprising observation by Farman, Gardiner and Shanklin [19] in 1985 that the springtime O3 hole appeared over Antarctica and at low altitudes of 15-20 km. It was subsequently found that the formation of the ozone hole is closely related to the existence of polar stratospheric clouds (PSCs) that form in the winter Antarctic stratosphere and
consist mainly of condensed-phase water ice or/and nitric acid ice [20, 21]. The O3 hole was then explained by mixed photochemical models [22-25]:
(1) the photolysis of CFCs occurs in the upper tropical stratosphere;
(2) air transportation to the lower polar stratosphere of inorganic halogen species (mainly HCl and ClONO2) resulting from reactions of CFC dissociation products (Cl and ClO) with other atmospheric molecules (CH4 and NO2)
(3) heterogeneous chemical reactions of inorganic halogen species on ice surfaces in PSCs to form photoactive Cl2 and HOCl in the winter lower polar stratosphere. Finally, the sunlight-photolysis of photoactive halogens produces Cl atoms to destroy ozone in the spring polar stratosphere. These are the widely accepted explanation of the O3 hole.
The Montreal Protocol has successfully phased out the production of CFCs in the world wide. Since the observed total halogen level in the troposphere peaked in ~1994, the original prediction was that “Peak global ozone losses are expected to occur during the next several years” [26]. The equivalent effective stratospheric chlorine levels at midlatitudes and Antarctica were then re-calculated to peak in the years around 1997 and 2000, respectively with delays of ~3 and ~6 years from the tropospheric peak, and it was thus predicted that the total O3 in mid-latitudes and the Antarctic O3 hole would have recovered correspondingly [27]. So far, however, no statistically significant recovery of O3 loss has been observed [28]. Even the largest Arctic ozone hole was observed in 2011 [29]. More remarkably, the largest (smallest) Antarctic O3 holes were observed when solar activity was weakest (strongest), e.g., in 1987, 1998 and 2008 (1991, 2002 and 2013 (expected)). In fact, there has been no O3 loss observed over the Equator in the past four decades. These observations are inconsistent with the above predictions from photochemical models and indicate that the current photochemical theory of ozone loss is incomplete or wrong. As noted recently by Manney et al. [29], the ability of current atmospheric/climate models to predict the future polar O3 loss is very limited, and improving the predictive capabilities is one of the greatest challenges in polar O3 research. To place the Protocol on a firmer scientific ground, it is still required to obtain a correct and complete ozone depletion theory.
The fact is also that parallel to the study of photolysis of CFCs, there is a long history of
studying electron-induced reactions of halogenated molecules including CFCs [30, 31]. The dissociative attachment (DA) of gaseous CFCs to low-energy free electrons was once suggested as a potential sink of CFCs in the atmosphere by Peyerimhoff et al. [32,
33]. But the process was long thought to be insignificant due to the low free electron density detected in the stratosphere [34, 35]. Then, the large enhancements by up to four orders of magnitude in electron-stimulated desorption of Cl- ions from CF2Cl2 adsorbed on polar molecular ice surfaces were surprisingly observed by Lu and Madey [5, 36-
39] and then confirmed by Solovev et al. [40]. In Lu and Madey experiments [5], electron-induced dissociation cross sections of CFCs adsorbed on polar ice surfaces were measured to be 106-108 times the photodissociation cross sections (10^-20 cm2) of gaseous CFCs [30], and a dissociative electron transfer (DET) mechanism was proposed to explain the results:
where et‾ is a weakly-bound electron trapped in the polar (H2O/NH3) ice [5, 36]. This unexpected finding revived the studies of electron-induced reactions of halogenated molecules. The DET mechanism of halogen-containing molecules was also confirmed in surface electron trapping experiments by Lu and Sanche [6, 41-43] and in surface photochemistry experiments by others [44, 45]. More recently, femtosecond time-resolved laser spectroscopic measurements have obtained direct observations of DET reactions of halogenated molecules in liquid water by Lu and co-workers [46-49] or adsorbed on solid ice surfaces by Ryu et al. [50] and Wolf and co-workers [51, 52]. Remarkably, Stähler et al. [52] have recently measured a very large DET dissociation cross section up to 4×10¯12 cm2 for CFCl3 on D2O ice, which is comparable to those observed for CF2Cl2 adsorbed on H2O and NH3 ice, being ~1×10¯14 and ~6×10¯12 cm2, respectively by Lu and Madey [5]. The DET mechanism has also been confirmed by several theoretical simulations [53-57].
In particular, ozone loss has shown strong spatial and time correlations with CR intensity.
The electron production rate by CRs has a maximum at an altitude of around 18 km in the lower polar stratosphere, at which the O3 hole is exactly observed. More remarkably, observed data have shown an 11-year cyclic variation of polar O3 loss, corresponding to the 11-year cycles of CR intensity. This is consistent with the prediction of the CRE mechanism, which is strikingly different from various photochemical model calculations predicting no 11-year cyclic variations in polar O3 loss [27, 28]. It should be noted that because the oscillation amplitude of the CR intensity in 11-year CR cycles was well-known to be small, only about 10% of its mean value, the resultant oscillation amplitude of polar O3 would be too small (far less than 5%) to observe if the CRE mechanism only played a minor role [14, 15].
Now to add to that series is this via WUWT:
Calculated
change in equilibrium surface temperature (ΔTs) (solid curve in green) due
solely to CFCs, HCFCs and CCl4, with a climate sensitivity factor α=0.9 K W-1m2
and a climate feedback amplification factor Β=2. Observed global surface
temperature data (bars) were from the UK Met Office Hadley Centre; the red
curve is a 3-point average smoothing of observed data (updated from Fig. 6 in
Lu [68]).
On
Cosmic-Ray-Driven Electron Reaction Mechanism for Ozone Hole
and Chlorofluorocarbon Mechanism for Global Climate Change
Qing-Bin Lu, Department of Physics and Astronomy, University of Waterloo
Qing-Bin Lu, Department of Physics and Astronomy, University of Waterloo
Abstract
Numerous laboratory measurements have provided a sound physical basis for the cosmic-ray driven electron induced reaction (CRE) mechanism of halogen-containing molecules for the ozone hole. And observed spatial and time correlations between polar ozone loss or stratospheric cooling and cosmic rays have shown strong evidence of the CRE mechanism [Q.-B. Lu, Phys. Rep. 487, 141-167(2010)]. Chlorofluorocarbons (CFCs) were also long-known greenhouse gases but were thought to play only a minor role in climate change. However, recent observations have shown evidence of the saturation in greenhouse effect of non-CFC gases. A new evaluation has shown that halocarbons alone (mainly CFCs) could account for the rise of 0.5~0.6 °C in global surface temperature since 1950, leading to the striking conclusion that not CO2 but CFCs were the major culprit for global warming in the late half of the 20th century [Q.-B. Lu, J. Cosmology 8, 1846-1862(2010)].
Surprisingly, a recent paper [J.-W. Grooß and R. Müller, Atmos. Environ. 45, 3508-3514(2011)] has criticized these new findings by presenting “ACE-FTS satellite data”. Here, I show that there exist serious problems with such “ACE-FTS satellite data” because the satellite has essentially not covered the Antarctic vortex in the presented months (especially winter months during which most effective CRE reactions are expected) and that the criticisms do not agree with the scientific facts in the literature. Instead, real data from multiple satellites provide strong evidence of the CRE mechanism. So far, the CRE mechanism is the only one that reproduces and predicts 11-year cyclic variations of ozone loss in the Antarctic O3 hole and of resultant stratospheric cooling, and the CFC mechanism can well explain both recent global warming and cooling. These findings should improve our understandings of the ozone hole and global climate change.
Introduction
Both natural and human effects could alter the Earth’s climate and environment. The ozone hole and global temperature change have been two major scientific problems of global concern. There is long interest in studying the effects of cosmic rays (CRs)
on Earth’s ozone layer [1-17]. In the 1970s, the odd nitrogen (NOx) generated by solar particle events (SPEs) were proposed first by Crutzen et al. [1] for solar proton events and then by Thorne [3] for energetic electron precipitation events to cause transient O3 destruction in the upper stratosphere at altitudes above 30 km. And Ruderman et al. [2]
proposed that the 11-year solar cycle variation of the CR intensity may also result in a small modulation (2~3% above or below the mean value) of polar total O3. However, the sink of O3 by SPEs, often associated with very large solar flares, is expected to be most pronounced during solar maxima and opposite in phase to the O3 loss caused by CRs [3].
If these natural effects were appreciable, they would lead to an 11-year cyclic variation in any season (e.g., summer). However, observed O3 data show no considerable long-term correlation between total ozone in the summer polar stratosphere and solar activity / CRs These natural effects are very limited in the long-term total O3 variation. Direct measurements based on balloons and satellites have shown convincing evidence that the formation of the O3 hole is related to human-made chlorofluorocarbons (CFCs) such as CF2Cl2 (CFC-12) and CFCl3 (CFC-11).
In 1974, Molina and Rowland first proposed that CFCs are decomposed by photodissociation with UV sunlight (a process called photolysis). The liberated chlorine atoms contribute to the depletion of the O3 layer. This photolysis was originally predicted to happen in the upper tropical stratosphere at high altitudes of ~40 km. Then it came with a surprising observation by Farman, Gardiner and Shanklin [19] in 1985 that the springtime O3 hole appeared over Antarctica and at low altitudes of 15-20 km. It was subsequently found that the formation of the ozone hole is closely related to the existence of polar stratospheric clouds (PSCs) that form in the winter Antarctic stratosphere and
consist mainly of condensed-phase water ice or/and nitric acid ice [20, 21]. The O3 hole was then explained by mixed photochemical models [22-25]:
(1) the photolysis of CFCs occurs in the upper tropical stratosphere;
(2) air transportation to the lower polar stratosphere of inorganic halogen species (mainly HCl and ClONO2) resulting from reactions of CFC dissociation products (Cl and ClO) with other atmospheric molecules (CH4 and NO2)
(3) heterogeneous chemical reactions of inorganic halogen species on ice surfaces in PSCs to form photoactive Cl2 and HOCl in the winter lower polar stratosphere. Finally, the sunlight-photolysis of photoactive halogens produces Cl atoms to destroy ozone in the spring polar stratosphere. These are the widely accepted explanation of the O3 hole.
The Montreal Protocol has successfully phased out the production of CFCs in the world wide. Since the observed total halogen level in the troposphere peaked in ~1994, the original prediction was that “Peak global ozone losses are expected to occur during the next several years” [26]. The equivalent effective stratospheric chlorine levels at midlatitudes and Antarctica were then re-calculated to peak in the years around 1997 and 2000, respectively with delays of ~3 and ~6 years from the tropospheric peak, and it was thus predicted that the total O3 in mid-latitudes and the Antarctic O3 hole would have recovered correspondingly [27]. So far, however, no statistically significant recovery of O3 loss has been observed [28]. Even the largest Arctic ozone hole was observed in 2011 [29]. More remarkably, the largest (smallest) Antarctic O3 holes were observed when solar activity was weakest (strongest), e.g., in 1987, 1998 and 2008 (1991, 2002 and 2013 (expected)). In fact, there has been no O3 loss observed over the Equator in the past four decades. These observations are inconsistent with the above predictions from photochemical models and indicate that the current photochemical theory of ozone loss is incomplete or wrong. As noted recently by Manney et al. [29], the ability of current atmospheric/climate models to predict the future polar O3 loss is very limited, and improving the predictive capabilities is one of the greatest challenges in polar O3 research. To place the Protocol on a firmer scientific ground, it is still required to obtain a correct and complete ozone depletion theory.
The fact is also that parallel to the study of photolysis of CFCs, there is a long history of
studying electron-induced reactions of halogenated molecules including CFCs [30, 31]. The dissociative attachment (DA) of gaseous CFCs to low-energy free electrons was once suggested as a potential sink of CFCs in the atmosphere by Peyerimhoff et al. [32,
33]. But the process was long thought to be insignificant due to the low free electron density detected in the stratosphere [34, 35]. Then, the large enhancements by up to four orders of magnitude in electron-stimulated desorption of Cl- ions from CF2Cl2 adsorbed on polar molecular ice surfaces were surprisingly observed by Lu and Madey [5, 36-
39] and then confirmed by Solovev et al. [40]. In Lu and Madey experiments [5], electron-induced dissociation cross sections of CFCs adsorbed on polar ice surfaces were measured to be 106-108 times the photodissociation cross sections (10^-20 cm2) of gaseous CFCs [30], and a dissociative electron transfer (DET) mechanism was proposed to explain the results:
where et‾ is a weakly-bound electron trapped in the polar (H2O/NH3) ice [5, 36]. This unexpected finding revived the studies of electron-induced reactions of halogenated molecules. The DET mechanism of halogen-containing molecules was also confirmed in surface electron trapping experiments by Lu and Sanche [6, 41-43] and in surface photochemistry experiments by others [44, 45]. More recently, femtosecond time-resolved laser spectroscopic measurements have obtained direct observations of DET reactions of halogenated molecules in liquid water by Lu and co-workers [46-49] or adsorbed on solid ice surfaces by Ryu et al. [50] and Wolf and co-workers [51, 52]. Remarkably, Stähler et al. [52] have recently measured a very large DET dissociation cross section up to 4×10¯12 cm2 for CFCl3 on D2O ice, which is comparable to those observed for CF2Cl2 adsorbed on H2O and NH3 ice, being ~1×10¯14 and ~6×10¯12 cm2, respectively by Lu and Madey [5]. The DET mechanism has also been confirmed by several theoretical simulations [53-57].
As
reviewed recently by Lu [15], it has now been well-established that polar media
in various (gas, liquid and solid) phases can largely enhance electron-induced
dissociations of both organic and inorganic halogenated molecules such as CFCs
and HCl (ClONO2) to various degrees via the DET reaction mechanism. It is also
well-known that copious electrons are produced by atmospheric ionization of
cosmic rays in the stratosphere, especially in the lower polar stratosphere
with the presence of PSC ice particles in the winter and early spring polar stratosphere. This logically led to the
search of the significance of DET reactions of halogenated molecules for O3
depletion in the polar stratosphere [5]. Oum et al. [58] had also reported that
Cl¯ ions can be converted into Cl2
molecules in atmospheric reactions of sea salts. Lu and Madey [5] therefore proposed the observed large enhancement of anions (Cl‾) from DET reactions of halogenated molecules adsorbed on PSC ice surfaces as an unrecognized mechanism for the formation of the O3 hole. It was proposed that resultant Cl‾ ions can either be rapidly converted to reactive Cl atoms to destroy O3 molecules, or react with other species at PSC ice surfaces to release photoactive Cl2 and ClNO2 in the winter (dark) polar stratosphere [5, 15]. The latter can also produce Cl atoms to destroy O3, upon photolysis in the spring polar stratosphere. Subsequently, numerous data from field measurements of total O3, CFCs, CRs as well as O3- loss induced stratospheric cooling over Antarctica over the past five decades were examined by Lu and Sanche [6] and Lu [14, 15]. These data have provided strong evidence of the cosmic-ray-driven electron-reaction (CRE) mechanism for the O3 hole.
molecules in atmospheric reactions of sea salts. Lu and Madey [5] therefore proposed the observed large enhancement of anions (Cl‾) from DET reactions of halogenated molecules adsorbed on PSC ice surfaces as an unrecognized mechanism for the formation of the O3 hole. It was proposed that resultant Cl‾ ions can either be rapidly converted to reactive Cl atoms to destroy O3 molecules, or react with other species at PSC ice surfaces to release photoactive Cl2 and ClNO2 in the winter (dark) polar stratosphere [5, 15]. The latter can also produce Cl atoms to destroy O3, upon photolysis in the spring polar stratosphere. Subsequently, numerous data from field measurements of total O3, CFCs, CRs as well as O3- loss induced stratospheric cooling over Antarctica over the past five decades were examined by Lu and Sanche [6] and Lu [14, 15]. These data have provided strong evidence of the cosmic-ray-driven electron-reaction (CRE) mechanism for the O3 hole.
In particular, ozone loss has shown strong spatial and time correlations with CR intensity.
The electron production rate by CRs has a maximum at an altitude of around 18 km in the lower polar stratosphere, at which the O3 hole is exactly observed. More remarkably, observed data have shown an 11-year cyclic variation of polar O3 loss, corresponding to the 11-year cycles of CR intensity. This is consistent with the prediction of the CRE mechanism, which is strikingly different from various photochemical model calculations predicting no 11-year cyclic variations in polar O3 loss [27, 28]. It should be noted that because the oscillation amplitude of the CR intensity in 11-year CR cycles was well-known to be small, only about 10% of its mean value, the resultant oscillation amplitude of polar O3 would be too small (far less than 5%) to observe if the CRE mechanism only played a minor role [14, 15].
In
addition to their well-known role in O3 depletion, CFCs are also long known
effective greenhouse (GH) gases [59-65]. These previous studies using various
climate models unfortunately concluded that halocarbons would play an important
but not dominant role in past and future surface temperature changes. In
current IPCC climate models [66, 67, 27, 28], it was generally thought that
halocarbons would play only a minor part in global warming, whose concentrations are orders of magnitude smaller than those
of non-halogenated gases (CO2, CH4 and N2O). The 2011 WMO Report [28] has
concluded that the positive radiative forcing ΔF due to the CFCs and HCFCs in
2008 was 0.34 ± 0.03 W/m², which represented only ~17% of the calculated ΔF of +1.7 W/m2 by
CO2, together with a small ΔF of about -0.05 ± 0.1 W/m2 due to stratospheric O3
depletion.
Full paper here
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