Chapter 1 Ozone-Depleting Substances (Odss) and Related Chemicals
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CHAPTER 1 Ozone-Depleting Substances (ODSs) and Related Chemicals Coordinating Lead Authors: Contributors: S.A. Montzka E. Atlas S. Reimann P. Bernath T. Blumenstock Lead Authors: J.H. Butler A. Engel A. Butz K. Krüger B. Connor S. O’Doherty P. Duchatelet W.T. Sturges G. Dutton F. Hendrick Coauthors: P.B. Krummel D. Blake L.J.M. Kuijpers M. Dorf E. Mahieu P. Fraser A. Manning L. Froidevaux J. Mühle K. Jucks K. Pfeilsticker K. Kreher B. Quack M.J. Kurylo M. Ross A. Mellouki R.J. Salawitch J. Miller S. Schauffler O.-J. Nielsen I.J. Simpson V.L. Orkin D. Toohey R.G. Prinn M.K. Vollmer R. Rhew T.J. Wallington M.L. Santee H.J.R. Wang A. Stohl R.F. Weiss D. Verdonik M. Yamabe Y. Yokouchi S. Yvon-Lewis CHAPTER 1 OZONE-DEPLETING SUBSTANCES (ODSs) AND RELATED CHEMICALS Contents SCIENTIFIC SUMMARY .............................................................................................................................................1 1.1 SUMMARY OF THE PREVIOUS OZONE ASSESSMENT ................................................................................7 1.2 LONGER-LIVED HALOGENATED SOURCE GASES ......................................................................................7 1.2.1 Updated Observations, Trends, and Emissions .........................................................................................7 1.2.1.1 Chlorofluorocarbons (CFCs) ......................................................................................................7 Box 1-1. Methods for Deriving Trace Gas Emissions ............................................................................14 1.2.1.2 Halons .......................................................................................................................................15 1.2.1.3 Carbon Tetrachloride (CCl4) .....................................................................................................16 Box 1-2. CCl4 Lifetime Estimates ...........................................................................................................18 1.2.1.4 Methyl Chloroform (CH3CCl3) .................................................................................................19 1.2.1.5 Hydrochlorofluorocarbons (HCFCs) ........................................................................................20 1.2.1.6 Methyl Bromide (CH3Br) .........................................................................................................23 1.2.1.7 Methyl Chloride (CH3Cl) ..........................................................................................................27 Box 1-3. Atmospheric Lifetimes and Removal Processes .....................................................................34 1.2.2 Loss Processes .........................................................................................................................................35 1.3 VERY SHORT-LIVED HALOGENATED SUBSTANCES (VSLS) ..................................................................37 1.3.1 Emissions, Atmospheric Distributions, and Abundance Trends of Very Short-Lived Source Gases.....37 1.3.1.1 Chlorine-Containing Very Short-Lived Source Gases .............................................................37 Box 1-4. Definition of Acronyms Related to Short-Lived Gases ..........................................................39 1.3.1.2 Bromine-Containing Very Short-Lived Source Gases .............................................................41 1.3.1.3 Iodine-Containing Very Short-Lived Source Gases .................................................................44 1.3.1.4 Halogen-Containing Aerosols ...................................................................................................44 1.3.2 Transport of Very Short-Lived Substances into the Stratosphere ...........................................................44 1.3.2.1 VSLS Transport from the Surface in the Tropics to the Tropical Tropopause Layer (TTL) ...45 1.3.2.2 VSLS Transport from the TTL to the Stratosphere ..................................................................46 1.3.2.3 VSLS Transport from the Surface to the Extratropical Stratosphere .......................................46 1.3.3 VSLS and Inorganic Halogen Input to the Stratosphere .........................................................................47 1.3.3.1 Source Gas Injection (SGI) .......................................................................................................47 1.3.3.2 Product Gas Injection (PGI) ......................................................................................................49 1.3.3.3 Total Halogen Input into the Stratosphere from VSLS and Their Degradation Products ........51 1.3.4 Potential Influence of VSLS on Ozone ...................................................................................................53 1.3.5 The Potential for Changes in Stratospheric Halogen from Naturally Emitted VSLS .............................54 1.3.6 Environmental Impacts of Anthropogenic VSLS, Substitutes for Long-Lived ODSs, and HFCs .........54 1.3.6.1 Evaluation of the Impact of Intensified Natural Processes on Stratospheric Ozone ................55 1.3.6.2 Very Short-Lived New ODSs and Their Potential Influence on Stratospheric Halogen ..........55 1.3.6.3 Evaluation of Potential and In-Use Substitutes for Long-Lived ODSs ....................................55 1.4 CHANGES IN ATMOSPHERIC HALOGEN ......................................................................................................63 1.4.1 Chlorine in the Troposphere and Stratosphere ........................................................................................63 1.4.1.1 Tropospheric Chlorine Changes ...............................................................................................63 1.4.1.2 Stratospheric Chlorine Changes ................................................................................................64 1.4.2 Bromine in the Troposphere and Stratosphere ........................................................................................66 1.4.2.1 Tropospheric Bromine Changes ...............................................................................................66 1.4.2.2 Stratospheric Bromine Changes ................................................................................................67 1.4.3 Iodine in the Upper Troposphere and Stratosphere .................................................................................73 1.4.4 Equivalent Effective Chlorine (EECl) and Equivalent Effective Stratospheric Chlorine (EESC) .........73 1.4.5 Fluorine in the Troposphere and Stratosphere ........................................................................................75 1.5 CHANGES IN OTHER TRACE GASES THAT INFLUENCE OZONE AND CLIMATE ...............................75 1.5.1 Changes in Radiatively Active Trace Gases that Directly Influence Ozone ...........................................76 1.5.1.1 Methane (CH4) ..........................................................................................................................76 1.5.1.2 Nitrous Oxide (N2O) .................................................................................................................79 1.5.1.3 COS, SO2, and Sulfate Aerosols ...............................................................................................80 1.5.2 Changes in Radiative Trace Gases that Indirectly Influence Ozone .......................................................81 1.5.2.1 Carbon Dioxide (CO2) ..............................................................................................................81 1.5.2.2 Fluorinated Greenhouse Gases .................................................................................................82 1.5.3 Emissions of Rockets and Their Impact on Stratospheric Ozone ...........................................................85 REFERENCES .............................................................................................................................................................86 ODSs and Related Chemicals SCIENTIFIC SUMMARY The amended and adjusted Montreal Protocol continues to be successful at reducing emissions and atmo- spheric abundances of most controlled ozone-depleting substances (ODSs). Tropospheric Chlorine • Total tropospheric chlorine from long-lived chemicals (~3.4 parts per billion (ppb) in 2008) continued to decrease between 2005 and 2008. Recent decreases in tropospheric chlorine (Cl) have been at a slower rate than in earlier years (decreasing at 14 parts per trillion per year (ppt/yr) during 2007–2008 compared to a decline of 21 ppt/ yr during 2003–2004) and were slower than the decline of 23 ppt/yr projected in the A1 (most likely, or baseline) scenario of the 2006 Assessment. The tropospheric Cl decline has recently been slower than projected in the A1 scenario because chlorofluorocarbon-11 (CFC-11) and CFC-12 did not decline as rapidly as projected and because increases in hydrochlorofluorocarbons (HCFCs) were larger than projected. • The contributions of specific substances or groups of substances to the decline in tropospheric Cl have changed since the previous Assessment. Compared to 2004, by 2008 observed declines in Cl from methyl chloroform (CH3CCl3) had become smaller, declines in Cl from CFCs had become larger (particularly CFC-12), and increases in Cl from HCFCs had accelerated. Thus, the observed change in total tropospheric Cl of −14 ppt/yr during 2007–2008 arose from: • −13.2 ppt Cl/yr