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Stratospheric Chemistry and
Processes
Sophie Godin-Beekmann
LATMOS, OVSQ, IPSL
1 MOSS, Reunion Island, 28 Nov. - 03 Dec. 2016
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The Stratosphere
2 MOSS, Reunion Island, 28 Nov. - 03 Dec. 2016
• Layer just above the troposphere
• Altitude depends on latitude and season (higher in the tropics and summer)
• ~10% of atmospheric mass
• Positive gradient of temperature due to solar UV radiation absorption by molecular oxygen and ozone
• Slow mixing in the vertical
• Chemical processes linked to the presence of ozone
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The ozone layer
3
Main properties of ozone
Ozone vertical distribution
90%
10%
• Absorbs UVB radiation 280 – 320 nm • Heats the stratosphere • Strong oxidant
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Ozone column abundance
All atmosphere molecules: ~8 km
All ozone molecules compressed to P ~1 atm. and T=0°C: Layer of 3 mm thickness (300 DU)
Ozone formation in the atmosphere ~500 millions years ago allowed life to emerge from the ocean
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Ozone equilibrium: chemical processes
4
O2
O2 + hn ® O + O
O + O2 + M ® O3 + M
O3 + hn ® O + O2
O + O3 ® 2 O2
Production
Loss
l < 242 nm
Chapman mechanism proposed in 1930 by Sydney Chapman
R1
R2
l < 310 nm R3
R4
(+DQ)
Chapman mechanism successful in reproducing general shape of ozone layer but: explains only 20% of the loss of Ox in the stratosphere
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Ozone loss: catalytic cycles
5
Catalytic cycles
Catalytic agents produced from source gases transported to the stratosphere by dynamic processes
N2O, CH4, H2O, CH3Cl, CH3Br
CFCs, Halons
R4 reaction (O + O3 -> 2O2) too slow in chapman mechanism:
Other mechanisms introduced to explain the loss of Ox via
O3+ X ® XO + O2
O + XO ® X + O2
net: O + O3 ® 2 O2
NOx
CH3Cl & CFCs: CF2Cl2
CF3Cl N2O
CH4
Methyl bromide
& Halons
H2O
HOx ClOx BrOx
Catalytic cycles can occur 1000 times
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Overview of chemical processes
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Example: NOx cycle
N2O + hn N2 + O1D R1 or N2O + O1D N2 + O2 R2 NO + NO R3
R3: only 5% of N2O loss but only source of NOx radicals
Catalytic cycle
NO + O3 NO2 + O2
NO2 + O NO + O2
Net O + O3 2 O2
Formation of reservoir species limits efficiency of the cycles: HO2 + HO2 H2O2 + O2 ClO + NO2 + M ClONO2 + M NO2 + OH + M HNO3 + M BrO + NO2 + M BrONO2 + M Cl + CH4 HCl + CH3
Rapid exchange of NO-NO2 NOx family
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Fragile ozone equilibrium
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abundance of radical species 44°N, zenith angle: 60° Reprobus model
Atmospheric abundance of main atmospheric species
Ozone controled by species 1000 time less abundant!!
HOx
NOx
ClOx
BrOx
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Efficiency of catalytical science
8
Efficiency of main catalytic cycles
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Ozone photochemical lifetime
Lower stratosphere: ozone controlled by dynamical processes
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Ozone equilibrium : dynamical processes
9
Brewer-Dobson circulation
Planetary waves
Total ozone climatology
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Mainly produced in the tropics, ozone is transported towards the poles by the meridional stratospheric circulation
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The perturbed ozone layer
10
Antarctic Ozone hole
October 2015
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First alerts on the ozone layer
11
1970s: controversy on the impact on ozone of a fleet of stratospheric supersonic transports
1974: article of Molina and Rowland
The SST project is abandoned (except for the UK-French Concord)
Catalytic destruction of ozone by chlorofluorocarbons (CFC)
1979: aerosol sprays are banned by USA, Sweden, Canada
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Substances depleting the ozone layer (SDO)
12
Chlorofluorocarbons (CFC)
• patent in 1928 by DuPont (USA) - Main CFC: CFC-11 (CCl3F), CFC-12 (CCl2F2)
• Long lifetime -> transported in the stratosphere by atmospheric dynamical processes
Halons
• Organic brominated gases • Main halons: halon-1211 and halon-1301 • Applications : dry cleaning, fire extinguishers
Natural sources of chlorine and bromine in the stratosphere CH3Cl (methyl chlorid) et CH3Br (methyl bromid): emitted by terrestrial and oceanic ecosystems.
• Applications : refrigeration, air conditioning, blowing agents ... wonder chemicals!
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Early 1980s
13
Evolution of knowledge on impact of CFCs on ozone
CFC emissions grow again...
But signature of the Vienna Convention for the protection of the ozone layer in 1985
Effect of CFC on ozone
First report on the state of the ozone layer
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Ozone hole discovery in Antarctica
Farman et al., Large Losses of total ozone in Antarctica reveal seasonal ClOx/NOx interaction, Nature, 1985
Syowa
At Syowa, total ozone and sonde measurements show also large decreases in Spring
Chubachi et al., QOS, 1984
14
TOMS Total Ozone monthly average
Stolarski et al., Nature, 1986
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Elucidation of ozone destruction mechanisms
15
NASA campaign: Airborne Antarctic Ozone expedition – 1987
ER-2 stratospheric plane
August September Before 1985 : Ozone theory based on chemical processes in gaseous phase only
Antarctica : ozone loss rate : ~5 % per day, not explainable by theory
Hypothesis :
Chemical reactions at the surface of polar stratospheric clouds:
• Activation of chlorine compounds(Solomon, 1986)
• Very fast catalytical cycles (Molina & Molina, 1987)
Scientific proof
pôle
ClO
O3
Anderson et al., 1991
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Polar ozone destruction mechanism
16
Ingredients for the formation of the ozone hole: 1. Increase chlorine and bromine content in the stratosphere (Cly x 5)
2. Isolated polar air masses in winter (polar vortex)
3. Very low temperatures(< - 80°C)
Complete total O3 destruction between 14 and 20 km
Cl2 + hn 2Cl
HOCl + hn OH + Cl
Cl + O3 ClO + O2
2060:12.8b:1/96:blm
In the light of therising spring sun
I n darkness
1
2
3
4
Formation of polarstratospheric clouds:
Formation of ClOx:
Activation of Clx: Catalyticozone depletion:
cold, isolatedpolar vortex
-80°C
Antarctica
H2O
HNO3 H2O
ClO + ClO Cl2O2
Cl2O2 + hn 2Cl + O2
Cl + O3 ClO + O2
ClONO2
HOCl
N2O5
Cl2,HOCl
HNO3
HCl
Stratosphere
Troposphere
9 km
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Polar stratospheric clouds
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Main PSC particles: Supercool ternary solution (STS), Nitric Acid trihydrate (NAT) and ice
CALIOP
Main heterogeneous reactions:
- Convert chlorine and bromine reservoir species into more reactive forms
- HCl, HNO3 and H2O remain in the particles
Peter, 2013
backscatter
depolarisation
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Polar chemistry
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Antarctic winter-spring 2006
Denitrification and dehydration observed by MLS
Main catalytic cycles ClO + ClO + M → ClOOCl +M BrO + ClO → Br + Cl + O
Cycles need ClO > 1 ppbv to be efficient
Destruction rate: ~5 % /day
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The Montreal Protocol
Signed in 1987 – entered into force in 1989
• Regulation of CFC and brominated halons emissions -> Substitutes less toxic for the ozone layer (First HCFC then second HFC that don’t contain chlorine)
• Technology transfer towards developing countries
• Regular reports on the state of the ozone layer and substitutes productions: the evolution of the protocol depending on scientific results
• Multilateral fund for technological transfers : ~ 4 billions dollars in 2014
• Reference for the creation of IPCC in 1988 related to climate change
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Montreal Protocol Amendments
« Science driven » protocol :
1996 2010
CFC
HCFC
2020 2040
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Ozone Destruction in the Arctic?
Formation of stratospheric clouds but polar vortex in the Arctic less isolated and warmer: polar ozone loss weaker and more variable
Polar Stratospheric Clouds
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Arctic ozone loss
22
Various international campaigns to quantify ozone loss : AASE, EASOE, SESAME, THESEO-SOLVE, RECONCILE Various measurements and methods (more difficult to distinguish chemical loss from dynamical loss): Match, passive ozone tracer
WMO, 2006
Arctic ozone loss in 1999/2000 compared to typical Antarctic ozone loss
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Chlorine activation in cold arctic winters
23
2005 2004/2005
AURA MLS measurements of HCl, ClO and O3 Santee et al., 2008
HCl ClO O3
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Ozone depletion at global scale
24
WMO, 1998
• No trends in the tropics • Mid-latitude ozone trends due to dilution of polar ozone loss, chemical in situ
processes and change in meteorology
Total ozone trends 1979 – 2000 Trend vertical profile 1980 – 1996
Fioletov et al., 2002
Ground-based Satellite
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Effect of volcanic stratospheric aerosols
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Increases sensitivity of ozone to ClOx and decreases sensitivity to NOx • High chlorine levels: decrease of O3
• Low chlorine: increase of O3
25
Pinatubo aerosol effect on ozone A few % temporary decrease
Mt Pinatubo eruption, June 1991
Significant injection of ~20 MT of SO2 that converted into H2SO4 aerosol droplets
El Chichon Pinatubo Lidar (Garmisch) Sage II
Main heterogeneous reactions on strat aerosols
Aerosol integrated backscatter 694.3 nm
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Present state of the ozone layer 27 years after enforcement of Montreal Protocol
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Evolution of CFC and halons content
27
EESC: Evolution of stratospheric halogen content weighted by the toxicity of species
towards ozone
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Evolution of Antarctic ozone hole
28
Ozone hole: Recurrent seasonal feature in Southern Hemisphere since 1980
Ozone hole area
Minimum d’ozone
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Ozone evolution at global scale
29
Annual ozone anomalies (with respect to 1998 – 2008 means)
WMO, 2014
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Evolution of polar ozone
30
Ozone minimum values in March (Arctic) and October (Antarctic)
Record Arctic ozone loss in 2011
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2002: major warming in Antarctica
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Record Arctic ozone depletion 2011
31
IASI total ozone
Manney et al., Nature 2011
also Sinnüber et al., 2012; Kuttipurath et al., 2012
25 % additional ozone loss due to denitrification Low ozone also explained partly by low ozone transport to the pole
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Looking for ozone recovery due to decrease of ODS
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Quantification of ozone variability
Multiple regression models
TOZ(t)=TOZ° + aEESCEESC(t)+Sai Proxyi(t) +
residual(t)
Main proxies used
- QBO (30 & 10 hPa)
- NAO or ENSO index
- Solar flux
- Eddy heat flux averaged over 45-75°N or 45-75°S (BDC)
- aerosol optical depth
- EESC or PWLT (piecewise linear trend with turning point around ~1996)
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Influence of proxies (polar regions)
34
Linear relationship between Spring/Fall ozone ratio and eddy heat flux Weber et al., 2011; Weber et al., 2012
± 4 DU
± 5 DU
± 10 DU
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Ozone recovery in Antarctica
35
Identification of second stage recovery claimed by Salby et al., GRL, 2011; JGR, 2011; Kuttipurath et al., 2013, and Knibbe et al., 2014
De Laat (2015) use « big data approach » to trace recovery, e.g. MC on period, proxy, etc..: 30–60% of the regressions result in statistically significant positive springtime ozone trend over Antarctica
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1st stage recovery 2nd stage recovery
Solomon et al., 2016 Significant recovery in September • increases in ozone
column amounts and vertical profile
• decreases in the area of the ozone hole
Yang et al., JGR, 2008
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Ozone recovery in the upper stratosphere?
Past changes in the vertical distribution of ozone : Analysis and interpretation of trends
Harris et al., ACP, 2015
error bars: black: std of weighted average red: Joint distribution
light blue: drifts taken into account
no significant upward trends different conclusion from WMO, 2014
NDACC Alpine station (OHP, Hohenpeissenberg, Bern) more than 2 decades of measurements
temporal instrumental artefacts vs geophysical signals: 3%/decade range in trends
Godin-Beekmann et al., 2016
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Global ozone trends
ODS decrease
Climate change effect:
Acceleration of Brewer-Dobson circulation
-> decrease of ozone in tropics
-> increase of ozone in extratropics
WMO, 2014
Evidence for an increase of the lower branch of the BDC :
Decrease of ozone in the LS in the 1980s (e.g. Randel and Thompson, 2011; Sioris et al, 2014, Shepherd et al., 2014) but:
• Hiatus in upwelling since 2002 from SAGEII + SCIAMACHY + SHADOZ ozone observations (Aschmann et al., 2014)
• Increase of ozone in the troposphere?
Contrasted trends observed in 2000 – 2013
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Main drivers of ozone long term changes
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Ozone changes and climate
• Sun drives radiative, dynamical and chemical processes affecting ozone and temperature
• Stratospheric temperature determined by concentrations of radiatively active gases (ozone, long-lived greenhouse gases, H2O) and aerosols via absorption of SW and LW radiation
• Transport determines amounts of stratospheric ozone and related long-lived compounds
• Temperature influences temperature-dependent reaction rates
transport
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Forecasted evolution of EESC
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Equivalent effective stratospheric chlorine
Total chlorine abundance at Jungfraujoch (x1015 mol.cm-2)
• Rate of decline depends on atmospheric lifetime of halogen compounds
• In the Polar regions age of air larger than in mid-latitude regions
• Return date to 1980 : Mid-latitudes ≈ 2040 – Polar regions ≈ 2065
Newman et al., acp, 2007
mid-latitudes Polar
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Source gases evolution
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IPCC 2007 WMO, GHG report 2015
2015 abundance relative to year 1750 of CH4 and N2O:
• CH4: 256% • N2O: 121% • CFC and HCFC abundances regulated by the Montreal Protocol
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Evolution of stratospheric aerosols
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• Tenfold increase of aerosols due to large volcanic eruptions (e.g. El Chichon, Pinatubo) induces a temporary ozone decrease (in the presence of large ODS levels)
• Since 2000: temporary increase of background aerosol due to small volcanic eruption
Vernier et al., GRL, 2011
SAOD 17-30km
Looking for new stratospheric aerosol background: volcanos vs impact of asian pollution
Khaykin et al., 2016
20°S – 20°N
NH mid-latitudes & OHP (44°N, 6°E)
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Radiative forcing (RF) of volcanic eruptions for the years 2008 – 2011 of ~ - 0.11 W m-2 (Solomon et al., 2011)
Non volcanic period: 17% increase
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Evolution of stratospheric temperature
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SSU temperature anomalies Global mean temperature anomalies from multiple data sets 10 – 25 km
• Global-mean lower stratosphere cooled by 1–2 K from 1980 to 1995
• Upper stratosphere cooled by 4–6 K from 1980 to about 1995.
• No significant long-term trend since 1995. • Cooling of stratosphere due to stratospheric
ozone depletion and GHG increase
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Effect of stratosphere cooling on ozone
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45°N for equinox conditions (end of March)
40 km 20 km
Homogeneous chemistry
Heterogeneous chemistry
Potential increase of PSC in polar regions Larger effect in the Arctic region (unsaturated ozone loss)
Slows ozone destruction rates, e.g. O + O3 → 2O2 at 40 km -> ozone increase
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Stratospheric water vapor
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• No recent increase in stratospheric water vapor at global scale
• Mechanisms driving long-term changes in stratospheric water vapor not well understood.
Effect on ozone
• Increase in HOx
• Increases temperature threshold for PSC formation in polar regions
Hartman et al., 2013, WMO, 2014
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Simulation of ozone recovery by climate models
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Future ozone evolution: summary
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ODS O3 destruction CO2 cools the stratosphere + impact on circulation (GHG) N2O O3 destruction (NOx cycle) CH4 O3 destruction + impact on circulation
Fleming et al., 2011, Portmann et al., 2012
Shepherd and Jonsson, acp, 2007
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Tropical regions
Eyring et al., JGR, 2013
• Ozone less sensitive to ODS
• Sensitive to BDC
• Decrease in stratosphere?
• Increase in troposphere?
• Observations?
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Polar ozone
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• Antarctic: return of October total column ozone to 1980 projected after mid century
• Arctic: return of March-mean Arctic total column ozone projected in 2020-2035
• Climate change dominates polar ozone evolution after 2050
• Larger sensitivity in NH
RCP: 8.5 6 4.5 2.6
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Some take home messages
• Montreal protocol successful in reducing the amount of ozone depleting substances (ODS) in the atmosphere but the return to pre-1980 levels will take decades
• The ozone layer should return to pre-1980 levels by 2020 – 2060 depending on latitudes and climate change effects
• Models predict by 2100 a super-recovery of ozone at mid-latitude and polar regions and an under-recovery in the tropics
• In the polar regions: competition between stratospheric cooling and decrease of ODS in the next decade. Also changes in meteorologic variability
• Future threat to the ozone layer: geoengineering by sulfate aerosols injection into the stratosphere
• Evaluation of future ozone levels needs an adequate ozone monitoring system: issues both in satellite and ground-based observing systems
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Polar Stratospheric Cloud observed at Haute-Provence Observatory on February 3, 2016
Thank you !
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