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									      Antarctic Ozone Hole Formation: Key Role of Photochemical Nonlinearity   1
         ESF REACTOR workshop “Nonlinear phenomena in chemistry”
                        Budapest, 24-27 January 2003



              Antarctic Ozone Hole Formation:
           Key Role of Photochemical Nonlinearity

                           Alexander M. Feigin
    Igor B. Konovalov, Michail Y. Kulikov, Anna Y. Mukhina

    Atmospheric Research Laboratory, Institute of Applied Physics,
      Russian Academy of Sciences, Nizhny Novgorod, Russia


                                   Content


           • Antarctic Ozone Hole: How does it look?

  • Why we can suggest a sufficient role of the nonlinearity?

  • Polar lower stratospheric photochemical system (PLS PCS):
                      description and specific features

     • Nonlinear dynamic properties (NDP) of the PLS PCS:
                    multistability and selfoscillations

           • Dynamic history of Antarctic ozone hole:
                      competition of bifurcations

• May the nonlinearity influence on future ozone hole evolution?
      What do we need to know for the correct prediction?



                          Atmospheric Research Laboratory
            Institute of Applied Physics of Russian Academy of Sciences
       Antarctic Ozone Hole Formation: Key Role of Photochemical Nonlinearity   2
          ESF REACTOR workshop “Nonlinear phenomena in chemistry”
                         Budapest, 24-27 January 2003


              Antarctic Ozone Hole: How does it look?


                            • Dobson Units (DU)

 characterize total ozone abundance in the atmosphere column
                                 (“overhead”)
1000 DU correspond to ozone abundance that forms under normal
                      conditions a 1 cm thick layer

                             • Ozone hole level:

            total ozone abundance is less than 220 DU
               (“normal” abundance is 350 – 400 DU)




                           Atmospheric Research Laboratory
             Institute of Applied Physics of Russian Academy of Sciences
Antarctic Ozone Hole Formation: Key Role of Photochemical Nonlinearity   3
   ESF REACTOR workshop “Nonlinear phenomena in chemistry”
                  Budapest, 24-27 January 2003




       Antarctic Ozone Hole: How does it look?



    Nimbus 7/ TOMS Total ozone for Oct 15, 1979




                     Atmospheric Research Laboratory
       Institute of Applied Physics of Russian Academy of Sciences
Antarctic Ozone Hole Formation: Key Role of Photochemical Nonlinearity   4
   ESF REACTOR workshop “Nonlinear phenomena in chemistry”
                  Budapest, 24-27 January 2003




       Antarctic Ozone Hole: How does it look?




                     Atmospheric Research Laboratory
       Institute of Applied Physics of Russian Academy of Sciences
Antarctic Ozone Hole Formation: Key Role of Photochemical Nonlinearity   5
   ESF REACTOR workshop “Nonlinear phenomena in chemistry”
                  Budapest, 24-27 January 2003




       Antarctic Ozone Hole: How does it look?


       • Vertical ozone profile over Antarctic:

    o season – averaged maximum of ozone layer over
       Antarctic Region is located at a height of 17-18 km

  o Antarctic ozone hole formation is mainly resulted from
     catastrophic ozone depletion in its season – averaged
                                maximum region




                     Atmospheric Research Laboratory
       Institute of Applied Physics of Russian Academy of Sciences
                      Antarctic Ozone Hole Formation: Key Role of Photochemical Nonlinearity                            6
                         ESF REACTOR workshop “Nonlinear phenomena in chemistry”
                                         Budapest, 24-27 January 2003



     Why we can suggest a sufficient role of the nonlinearity?

 • Atmospheric chemistry is “of nonlinear origin” due to be- and
                     three body reactions

                                   • Indirect observational evidences

Key ozone hole characteristic – minimal ozone concentration in
     region of season-averaged maximum of ozone layer
                                                       and
  One of key control parameters of polar lower stratospheric
photochemical system – concentration of inorganic chlorine Cly
                                     as function of time (in years)

                       30                                                                         8

                                                                                 O3
                                                                                 Cly
                                                                                                  6

                       20
                                                                                                      Clyx 10-9(cm-3)
  O3x 10-11 (cm-3 )




                                                                                                  4



                       10
                                                                                                  2




                        0                                                                         0

                            1976          1980            1984           1988              1992
                                           Atmospheric Research Laboratory
                             Institute of Applied Physics of Russian Academy of Sciences
        Antarctic Ozone Hole Formation: Key Role of Photochemical Nonlinearity   7
           ESF REACTOR workshop “Nonlinear phenomena in chemistry”
                          Budapest, 24-27 January 2003




     Why we can suggest a sufficient role of the nonlinearity?



We need to study nonlinear dynamic properties of the Polar Lower
 Stratospheric PhotoChemical System (PLS PCS) during Antarctic
                             ozone hole formation




Nonlinear Dynamic Properties (NDPs) are defined as possible type
 of behaviour (equilibriums, self-oscillations, chaotic oscillations of
different kinds) of the system under different combinations of control
                                    parameters




  Nonlinear Dynamic Properties (NDPs) may be investigated by a
  study of asymptotic (for        t → ∞ ) structure of the system phase
                                        space




                             Atmospheric Research Laboratory
               Institute of Applied Physics of Russian Academy of Sciences
         Antarctic Ozone Hole Formation: Key Role of Photochemical Nonlinearity   8
            ESF REACTOR workshop “Nonlinear phenomena in chemistry”
                           Budapest, 24-27 January 2003




Polar lower stratospheric photochemical system (PLS PCS) during
 Antarctic ozone hole formation: description and specific features

                            • Reactions and components:
                     48 reactions between 25 components

                     Reactions                   Rate of reactions
  (R1)     ClNO3+HCl(c)→Cl2+HNO3(c)             (R1) – (R4) are
  (R2)    ClNO3+H2O(c)→HOCl+HNO 3(c)             heterogeneous
  (R3)       HOCl+HCl(c)→Cl2+H2O(c)                reactions,
  (R4)       N2O5+H2O(c)→2HNO3(c)    (c) – condense (solid or liquid) state
  (R5)          O+O2+M→O3+M                          1.7×103
  (R6)             O+O3→2O2                  8.0×10-12exp(-2060/T)
  (R7)           O(1D)+M→O+M                  6.7×10-12exp(70/T)+
                                              1.4×10-11exp(110/T)
  (R8)             O2+hν→2O           2.9×2.6S×10-14, S=3.2×10-2×(d-20)
  (R9)          O3+hν→O2+O(1D)                        1×10-5
 (R10)           O3 +hν→O2+O                          3×10-4
 (R11)          H2O+O(1D)→2OH                       2.2×10-10
 (R12)          H2+O(1D)→H+OH                       1.0×10-10
 (R13)            OH+O→H+O2                   2.2×10-11exp(120/T)
 (R14)          HO2 +O→OH+O2                  3.0×10-11exp(200/T)
 (R15)          H+O2+M→HO2+M                        2.4×10-13
 (R16)           H+O3 →OH+O2                  1.4×10-10exp(-470/T)
 (R17)          OH+O3→HO2+O2                  1.6×10-12exp(-940/T)
 (R18)         HO2+O3 →OH+2O 2                1.1×10-14exp(-500/T)
 (R19)           H+HO2→H2+O2                        5.6×10-12
 (R20)         OH+HO 2 →H2O+O2                4.8×10-11exp(250/T)
 (R21)          OH+OH→H2O+O                   4.2×10-12exp(-240/T)
 (R22)         O(1D)+CH4→CH3+OH                     1.4×10-10
 (R23)          NO2 +O→NO+O2                  6.5×10-12exp(120/T)
 (R24)         NO+O3 →NO2 + O2               2.0×10-12exp(-1400/T)
 (R25)         NO+HO 2→NO2 +OH                3.7×10-12exp(250/T)
 (R26)        NO2+OH+M→HNO3+M                         9.5×10-12

                              Atmospheric Research Laboratory
                Institute of Applied Physics of Russian Academy of Sciences
           Antarctic Ozone Hole Formation: Key Role of Photochemical Nonlinearity        9
              ESF REACTOR workshop “Nonlinear phenomena in chemistry”
                             Budapest, 24-27 January 2003

                     • Reactions and components (continued):

                        Reactions                                  Rate of reactions
   (R27)            NO2+O3→NO3+O2                              1.2×10-13exp(-2450/T)
   (R28)         NO2+NO 3 +M→N2O5+M                                   1.5×10-12
   (R29)         HNO3+OH→NO3+H2O                                      5.8×10-13
   (R30)            NO+NO 3 →2NO2                               1.5×10-11exp(170/T)
   (R31)            NO2+hν→NO+O                                        9×10-3
   (R32)            NO3+hν→NO2+O                                       4×10-2
   (R33)          HNO3+hν→OH+NO 2                               10-7+5.7×10-9×(d-20)
   (R34)          N2O5+hν→NO3+NO 2                            6×10-6+1.1×10-7×(d-20)
   (R35)             Cl+O3 →ClO+O2                              2.9×10-11exp(-260/T)
   (R36)             ClO+O→Cl+O2                                 3.0×10-11exp(70/T)
   (R37)           ClO+NO→Cl+NO 2                               6.4×10-12exp(290/T)
   (R38)            Cl+HO 2 →HCl+O2                             1.8×10-11exp(170/T)
   (R39)             Cl+H2 →HCl+H                              3.7×10-11exp(-2300/T)
   (R40)            HCl+OH→H2O+Cl                               2.6×10-12exp(-350/T)
   (R41)         ClO+NO 2+M→ClNO3+M                                   1.4×10-12
   (R42)        ClO+ClO+M→ClOOCl+M                                    1.6×10-13
   (R43)           Cl+CH4→HCl+CH3                              1.1×10-11exp(-1400/T)
   (R44)          ClO+HO 2→HOCl+O2                              4.8×10-13exp(700/T)
   (R45)          ClOOCl+hν→ 2Cl+O2                          9.3×10-4+9.6×10-6×(d-20)
   (R46)             Cl2+hν→Cl+Cl                               1.4×10-3+(d-20)×10-5
   (R47)           ClNO3+hν→Cl+NO 3                           3×10-5+4.7×10-7×(d-20)
   (R48)           HOCl+hν→OH+Cl                              1.1×10-4+1.3×10-6×(d-20)

Constants for the rates of bimolecular and three body reactions (except for
(R5)) are given in cm3/s. The rate of (R5) reaction is in s -1. Constants for the
rates of three body reactions are calculated for the modeled conditions:
M=2.2×1018 cm3, T=192oK. Values of photodissociation coefficients are given
in s -1, d is the number of the day counted off from August 1

           • 48 reactions between 25 components !!! ⇒ we need to
                        construct basic dynamical model
           • Basic Dynamical Model (BDM) is simplified model, which
                  retains all the nonlinear dynamical properties of
             corresponding “full” model for interesting for us ranges of
                                  parameters’ values
                                Atmospheric Research Laboratory
                  Institute of Applied Physics of Russian Academy of Sciences
        Antarctic Ozone Hole Formation: Key Role of Photochemical Nonlinearity   10
           ESF REACTOR workshop “Nonlinear phenomena in chemistry”
                          Budapest, 24-27 January 2003

Polar lower stratospheric photochemical system (PLS PCS) during
 Antarctic ozone hole formation: description and specific features
  • Specific nonlinearity introduced by heterogeneous reactions

                • Distinctions of Transport processes:
    o Vertical and latitudinal transport is very slow (characteristic
       transport time is longer than “life time” of phenomenon)
     o Zonal (longitudinal) transport – rotation of the air around the
           pole – is much faster than phenomenon duration

                                           ⇓
  We have every reason to use zero-dimensional model for
      zonal-averaged description of the phenomenon
                   • Non-autonomy of the PLS PCS:
Several control parameters depend on time with characteristic time
scale, which is close to the characteristic time of the phenomenon

                                           ⇓
    The phenomenon (Antarctic ozone hole formation) is a
         transient process with limited “time of life”

                                           ⇓
   We need to study not only nonlinear dynamic properties (i.e.
asymptotic characteristics!) of PLS PCS, but to investigate has the
 system sufficient time “to feel” influence of bifurcations happened

                                           ⇓
        We need to think up a method of such investigation




                             Atmospheric Research Laboratory
               Institute of Applied Physics of Russian Academy of Sciences
       Antarctic Ozone Hole Formation: Key Role of Photochemical Nonlinearity   11
          ESF REACTOR workshop “Nonlinear phenomena in chemistry”
                         Budapest, 24-27 January 2003

                            Setting up a problem:


                        • Modeled period of time:

  From the middle of August till the middle of October (period of
                     Antarctic ozone hole formation)


                              • Modeled region:

    o Latitudes of (70 – 80)0 S (interior of Antarctic circumpolar
                                          vortex)

  o Altitudes of 17-18 km (location of season-averaged maximum
                                    of ozone layer)

   • Total number of oxygen, hydrogen, nitrogen, and chlorine
                        species involved in the BDM:

                                   Twenty five

                    • Total number of the reactions:

                                   Forty eight
   including four heterochemical reactions running within/on the
     surface of particles of type 1 Polar Stratospheric Clouds

        • Characteristic time scale of the phenomenon :

Ozone lifetime in the period of ozone hole formation ≈ (105 – 106) s



                            Atmospheric Research Laboratory
              Institute of Applied Physics of Russian Academy of Sciences
        Antarctic Ozone Hole Formation: Key Role of Photochemical Nonlinearity   12
           ESF REACTOR workshop “Nonlinear phenomena in chemistry”
                          Budapest, 24-27 January 2003

        Nonlinear dynamic properties (NDP) of the PLS PCS:
                       multistability and selfoscillations


      • Approach to investigation of NDP of the PLS PCS:
          construction of basic dynamical model

        • Basic Dynamical Model (BDM)of the PLS PCS:

                      o Evolution (“slow”) variables:

                 Concentrations of O3, HNO3 and HCl

                                           ⇓
  BDM of polar lower stratospheric PCS is a set of three ordinary
                            differential equastions

                                           ⇓
We need to investigate structure of three-dimensional (only!) phase
                                        space

                   o Control parameters of the BDM:

                           Ø “Autonomous” parameters:

 Concentrations Cly (inorganic chlorine family), NOy (odd nitrogen
family), sulfuric acid H2SO4, water vapor H2O, and season-averaged
                                 temperature Ts
Autonomous parameters can undergo trends from year to year and
   can be considered as the constants during current ozone hole
                                     formation
                             Atmospheric Research Laboratory
               Institute of Applied Physics of Russian Academy of Sciences
        Antarctic Ozone Hole Formation: Key Role of Photochemical Nonlinearity   13
           ESF REACTOR workshop “Nonlinear phenomena in chemistry”
                          Budapest, 24-27 January 2003

        Nonlinear dynamic properties (NDP) of the PLS PCS:
                       multistability and selfoscillations

                        Ø “Nonautonomous” parameters:

  Light day duration      τ , zenith solar angle Z, and daily-averaged
                                 temperature Td
  Nonautonomous parameters are considered as monotonically
  increased prescribed time functions τ (t), Z(t), and Td(t), which
correspond to actual changes of τ , Z, and Td during the ozone hole
                                     formation

                                           ⇓

    BDM of polar lower stratospheric PCS is nonautonomous

                                           ⇓
   The system can bifurcate not only from year to year (due to
  variations of the Cly, NOy, H2SO4, H2O, and Ts), but also in the
   course of the ozone hole formation in a definite year (due to
                    seasonal trends of τ , Z, and Td )

                                           ⇓
Necessity of preliminary analysis of modification of the BDM phase
  space structure from day to day (i.e. for values of τ , Z, and Td,
 corresponding to successive day numbers during the ozone hole
formation) for different sets of the autonomous control parameters
                       Cly, NOy, H2SO4, H2O, and Ts

                             Atmospheric Research Laboratory
               Institute of Applied Physics of Russian Academy of Sciences
          Antarctic Ozone Hole Formation: Key Role of Photochemical Nonlinearity   14
             ESF REACTOR workshop “Nonlinear phenomena in chemistry”
                            Budapest, 24-27 January 2003
Dynamic history of Antarctic ozone hole: competition of bifurcations
 Changes of phase space structure of the polar lower stratospheric
                  PCS during Antarctic Spring
Projection of three – dimensional phase trajectory, corresponding to
  the certain fixed day of evolution, onto the plane (O3) – (HNO3)

                              •      Pre-hole situation




+    State of the system
    in the corresponding day

• Stable equilibrium state

o Unstable equilibrium state




        1980, heterochemistry on the NAT particle surface:
(a) Phase trajectories 1,2, and 3 correspond to August 30th, September
                       14th and 23rd, respectively
         (b) Phase trajectory corresponding to September 26th
             (c) Phase space structure for September 27th
                               Atmospheric Research Laboratory
                 Institute of Applied Physics of Russian Academy of Sciences
          Antarctic Ozone Hole Formation: Key Role of Photochemical Nonlinearity                                    15
            ESF REACTOR workshop “Nonlinear phenomena in chemistry”
                            Budapest, 24-27 January 2003
Dynamic history of Antarctic ozone hole: competition of bifurcations
 Changes of phase space structure of the polar lower stratospheric
                  PCS during Antarctic Spring
Projection of three – dimensional phase trajectory, corresponding to
  the certain fixed day of evolution, onto the plane (O3) – (HNO3)

                               • Boundary situation:

                                                                12
                                                                         1




                                                                             2

                                                                8

                                                    HNO3,ppbv

+    State of the system
                                                                                                        3
    in the corresponding day                                    4




                                                                0
                                                                     0           1       2      3               4
                                                                                     O3,ppmv

       Phase trajectory corresponding to October 12th of 1885
           (heterochemistry on the NAT particle surface)

                  • Situation with well pronounced hole:
                                                                         1
                                                                12



× - Equilibrium states:
                                                                             2

     #1 is stable focus                                          8
                                                    HNO3,ppbv




     #2 is saddle-node                                                                                      3


     #3 is stable node                                           4




                                                                 0
                                                                     0           1        2         3               4
                                                                                     O 3,ppmv

       Phase trajectory corresponding to October 12th of 1887
           (heterochemistry on the NAT particle surface)
                               Atmospheric Research Laboratory
                 Institute of Applied Physics of Russian Academy of Sciences
      Antarctic Ozone Hole Formation: Key Role of Photochemical Nonlinearity                     16
         ESF REACTOR workshop “Nonlinear phenomena in chemistry”
                        Budapest, 24-27 January 2003
May the nonlinearity influence on future ozone hole evolution? (I)
            • Expected trends of the control parameters

                                     2000 2010 2020 2030 2040 2050
                               4.0                                   -4.0




                                                                            Ts decreasing, 0 K
                               3.0                                   -3.0
                 (Cly), ppbv




                               2.0                                   -2.0


                               1.0                                   -1.0


                               0.0                                   0.0
                                     2000 2010 2020 2030 2040 2050
                                              time, years

  • Possible “qualitative” consequences of the parameter trends
 Change of dominating type of Polar Stratospheric Clouds
                         (PSC)

Type 1a PSC formed by
  frozen NAT crystals
                                              ⇒             Type 1a PSC formed by
                                                              liquid STS particles

                                                ⇓
                   Change of the type of nonlinearity

                                                ⇓
                               Possibility of new bifurcations

                                                ⇓
            Specific scenarios of ozone hole evolution



                           Atmospheric Research Laboratory
             Institute of Applied Physics of Russian Academy of Sciences
                          Antarctic Ozone Hole Formation: Key Role of Photochemical Nonlinearity                                     17
                             ESF REACTOR workshop “Nonlinear phenomena in chemistry”
                                            Budapest, 24-27 January 2003

May the nonlinearity influence on future ozone hole evolution? (V)

          • Possible future scenarios of ozone hole formation under STS
                                  cloud conditions
                    (A)                                 (B)
                         2000 2010 2020 2030 2040                  2050                                 2000   2010 2020 2030 2040 2050

                    2                                                     2                       0.5                                     0.5


                   1.5                                                    1.5
  (O3 )min, ppmv




                                                                                (O3) min, ppmv
                    1                                                     1                      0.25                                     0.25


                   0.5                                                    0.5


                    0                                                     0                        0                                      0
                         2000 2010 2020 2030 2040                  2050                                 2000   2010 2020 2030 2040 2050
                                    time, years                                                                       time, year s

                                                                     (C)
                                                           2000 2010 2020 2030 2040                      2050
                                                   1.5                                                          1.5
                                       (O3)min, ppmv




                                                       1                                                        1




                                                   0.5                                                          0.5




                                                       0                                                        0
                                                           2000 2010 2020 2030 2040                      2050
                                                                    time, years
  (A), (B), and (C): Dependence of minimal ozone concentration
(O3)min in the region of season – averaged maximum of ozone layer
on year number for (A), (B), and (C) scenarios of denitrification and
                       dehydration, respectively

                                               Atmospheric Research Laboratory
                                 Institute of Applied Physics of Russian Academy of Sciences
         Antarctic Ozone Hole Formation: Key Role of Photochemical Nonlinearity   18
            ESF REACTOR workshop “Nonlinear phenomena in chemistry”
                           Budapest, 24-27 January 2003




                                    References


1. A.M.Feigin and I.B.Konovalov, “On the possibility of complicated
   dynamic behavior of atmospheric photochemical systems: Instability of
   the Antarctic photochemistry during the ozone hole formation”, J.
   Geophys. Res., 1996, v.101, n.D20, p.26,023-26,038.
2. A.M.Feigin,    I.B.Konovalov,    and     Y.I.Molkov,  “Toward     an
   understanding of the nonlinear nature of atmospheric photochemistry:
   Essential dynamic model of the mesospheric photochemical system”, J.
   Geophys. Res., 1998, v.103, n.D19, p.25,447-25,460.
3. I.B.Konovalov, A.M.Feigin and A.Y.Mukhina, “Toward an
   understanding of the nonlinear nature of atmospheric photochemistry:
   Multiple equilibrium states in the high-latitude lower stratospheric
   photochemical system”, J. Geophys. Res., 1999, v.104, n.D3, p.3,669-
   3,689.
4. M.Y.Kulikov, A.M.Feigin, “Nonlinear dynamic properties of polar
   stratospheric photochemistry in the presence of 1b polar stratospheric
   clouds and their influence on characteristics of the Antarctic ozone
   hole”, Preprint of IAP RAS #604, 2002, 32p. (in Russian).
5. A.M.Feigin, “Nonlinear dynamic models of atmospheric photochemical
   systems: methods for construction and analysis (Review)”, News of
   Russian Academy of Sciences: Physics of Atmosphere and Ocean,
   2002, v.38, n.5, p.581-628 (in Russian; to be translated in English and
   published in USA).




                              Atmospheric Research Laboratory
                Institute of Applied Physics of Russian Academy of Sciences

								
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