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Longterm trends of tropospheric ozone: A critical review critical
Johannes Staehelin
Institute for Atmospheric and Climate Science Swiss Federal Institute of Technology ZÝrich Including unpublished results of Christina Schnadt Poberaj


1. Introduction: Ozone in the Introduction: in atmosphere
C.F. SchÆnbein: Discovery of O3 (1840)
SchÆnbein in ,,Abhandlungen der zweiten Klasse der Bayrischen Akademie der Wissenssch., 1840":

When he was a 12 year old boy a ligthning stroke hit the church in Menzingen (where he grew up): ,,Because the door of the church was open, I entered the church (together with other persons) immediatley after the lightning stroke and I realized a particular smell (ziemlich stark ti li t stechenden Geruch, den ich damals auch fÝr schwefelicht erklÄrte) which I thought to be sulfur (sulfuric ?) "


- C.F. SchÆnbein (1842): Ozone present in ambient air -Many studies with SchÆnbein papers in 19th - Critics of method: Fox, 1873 - World War II: Photooxid. pollut. Los Angeles Area - Until end of 1960s: Tropospheric ozone budget (almost entirely) determined by flux from the y) stratosphere (Junge, 1963) -1970s: Numerical modelling: Levy (OH) - Modelling (Chameides and Walker, 1973, 1976; Crutzen, 1971): Chemical ozone production global influence ? - today: (additional) interest because of climatic effects (greenhouse gas), intercontinental transport


AR4


Overview
2. Processes and (anthropogenic) precursor emission changes 3. Regional ozone trends (Southern California and Mexico City) 4. Ozone in Europe until the early 1990 5. Trends in UT/LS over northern mid-latitudes from late 1970s to late 1990s (GASP, MOZAIC and ozone sondes) 6. Trends since early 1990s in northern mid-latitudes Trends mid 7. Trends in North America 8. Trends in Tropics Trends 8. Conclusions and open questions


2. Processes and (anthropogenic) precursor emisson changes
Tropospheric Photochemistry
Termination by NOx

sun

Initiation ROx: Photolysis of O3, Aldehydes, HONO + RCH3 (ROG)

HNO

Subtraction

3

OH
O RCO

+ CO + RCHO CO H2O RCO +O
2 2

H2O

or Addition

RCH2 (OH) H +O +O
2 2

O +O
2

+ O2 RCH2O

+ O2

O3
Termination by ROx + ROx

CO2 HO2 RCH2O2
2

O RCO2 NO2

H2O2 + HO2 + HO RCH2OOH

PAN's


Present global tropospheric ozone budget (in tg O3 y-1), Stevenson et al., 2006 (from 25 numerical simulations) for comp. [TAR] · Global photochemical ozone production (from anthropog. and natural precursors): 5056 (± 571) [3420] · Global photochemical ozone destruction: 4561 (± 722) [3470] · Surface destruction: 1014 (± 219) [770] · Import from stratosphere: 519 (±195) [770]


Emission changes: Fossil fuel related NOxemissions from continents (TEAM (TNO emission continents (TNO emission assessm. model), RETRO, Pulles et al., 2007.)


3. Regional ozone trends
PBL in Southern California th (Grosjean, Atmosph.Env., 2003)


Large emission decrease in emission in Southern California (VOC) (VOC)
4000 VOC NO
x

3000 Emissions (t/d)

2000

1000

0 1987 1997 2010 on-road 1987 other anthro 1997 2010


Ozone maxima at Mexico city


4. Ozone trends in Europe: Ozone World War II until 1990
· 19th century: SchÆnbein paper measurements: not reliable: Influence from humidity, non linear fl idi response to ozone dose · Montsouris measurements (close Paris) 1876-1911 Representativity ? SO2 influence completely removed ? · First half of 20th century: Chemical measurements (KI), mostly Europe, interference from SO2 and other compounds (small at remote sites)


Arosa (Swiss Alps, 1800 msl.): 1950-1990


Comparison of available historical data with measurements 1988-1991 (Europe)


NOx and NMVOC emissions of Western NMVOC Europe (T. Pulles et al., 2007)


5. Trends in UT/LS over northern midlatitudes from late 1970s - late 1990s
Measurements from ozone sondes (light balloons): start: red: (late) 1960s; green: 1970s; blue: 1980s


Ozonesonde measurements available for comparison with GASP/MOZAIC
Station Uccle Hohenpeissenberg Payerne Wallops Island ll Country Belgium Germany Switzerland USA Lat (°N) Lon (°) 50.8 47.8 49.49 37.93 4.35 35 11.02 6.57 -75.48 Total Number 644/1080 406/900 533/1162 188/970 Sensor BM (*) BM BM ECC

· BM sonde data have been used with correction factors (CF) applied ti (CF) li · Range of allowed CF: 0.9-1.35 (Uccle, Payerne), and 0.9-1.2 (Hohenpeissenberg) · Wallops Island Data normalised using SBUV column ozone information consistent for the whole 1975-2001 period, allowed CF range: 0.8-1.2 the allowed CF range: · Sonde data have been corrected for response time of the ozone and pressure sensors


Regular measurements from passenger aircraft
GASP: Global Atmospheric Sampling Program (see Schnadt Poeberaj et al., ACP, 2007) MOZAIC: The Measurement of Ozone and Water Vapor The Vapor by Airbus In-Service Aircraft Program
GASP (1975-1979)
Aircraft Species Altitude Range # Flights # Flight Hours Flight Ozone Instrument Measurement range Instrument Precision Uncertainty 4 commercial B-747 and the NASA CV-990 research aircraft O3, H2O, CO, NO, aerosols, and condensation nuclei 6-13.7 km 6149 14200 Continuous ultraviolet ozone photometer 3 to 1000 ppbv ± 1% or 3 ppbv, whichever is greater 8.4% or 3.3% (depending on diaphragm material). For very low O3 concentrations: 3 ppbv 5s averages every 5 to 10 minutes

MOZAIC (1994-2001)
5 commercial Airbus A340 O3 and H2O 9-12 km 14558 113008 Dual beam UV absorption 3 to 20000 ppbv 2 ppbv ± [2 ppbv + 2%]

Temporal Resolution

1 minute averages (measurements every 4s)


Flight Routes GASP (Global Atmospheric Sampling Program) and MOZAIC (Measurement of Ozone and Water Vapor by Airbus InService Aircraft)

GASP (1975-1979) (1975

MOZAIC (1994-2001)


Method of data analysis
· Interpolate ERA40 dynamical tropopause (2 PVU) information onto GASP, MOZAIC, and ozonesonde coordinates · Average GASP and MOZAIC tropospheric data ( < 0) over 10°x10° grid and compute differences · Comparison of long-term changes by aircraft and ozonesondes: - Average GASP/MOZAIC data over Europe (35°N-55°N, 10°W-30°E) and USA East (30°N-50°N, 90°W-60°W) regions and compute differences. - Average ozonesonde data over 1975-79 and 1994-2001 periods and compute differences


Upper Troposphere
Definition of regions for climatological means
Region 1: USA West 2: USA Northeast 3: Atlantic 4: Europe 5: North. India 6: South. India 7: South China 8: North. Japan 9: South. Japan 10: East Pac. ML 11: East Pac. ST ST
South-North

East-West 125°W-90°W 90°W-60°W 60°W-10°W 10°W-30°E 60°E-90°E 60°E-90°E 90°E-130°E 115°E-170°E 115°E-170°E 125°W-160°W 125°W-180°

30°N-50°N 40°N-50°N 40°N-60°N 35°N-55°N 30°N-40°N 20°N-30°N 5°N-25°N 40°N-50°N 30°N-40°N 30°N-50°N 10°N-30°N

Colours: GASP JJA upper troposphere ozone climatology

Regions 1, 10 and 11: GASP climatologies only


Climatology UT ozone GASP/MOZAIC

Red: GASP; blue: MOZAIC Schnadt Poberaj et al., 2007


Ozone changes in the upper troposphere: second part of 1970s vs. second part of 1990s
MOZAIC-GASP (%/decade)

Hatched boxes: differences significant (95%); Grey triangles: GASP data biased toward 1 year ( 50% from 1 year); Green triangles: GASP data only from 3 years
Differences only displayed if GASP data available from 3 years and ensemble size 10


Changes in anthropogenic NOx emissions from fossil fuel burning from continents between second half of 1970s and continents second half of 1990s (from TEAM model)

-150 -120 -90

-60

-30

0

30

60 60

90 90

120 150
3.0

80 70 60 50 40 30 20 10 0 40 10

10 20 30 40 50 60 70 80

2.0 1.8 1.6 1.4 1.2 1.0 0.8 0.6 0.4 0.2

Latitude

-150 -120 -90

-60

-30

0

30

60

90

120 150

Longitude


Relative differences climatological UT ozone profiles ( < 0, 3 < 100 ppb) (in %/dec.) between 75-79 and %/dec.) between 94-01 of aircraft and sonde data over Europe at potential temp. distance from 2 PVU tropopause (GASP and distance tropopause (GASP and MOZAIC averaged over Europe)
DJF MAM Black: MOZAIC-GASP Blue: Uccle Uccle Yellow: Hohenpeiss.berg ber JJA SON Red: Payerne Horizontal bars: 95% conf. intervalls intervalls of differences


6. Ozone since early 1990s in Europe (except Kislovosk) and North America k) th
BrÆnnimann et al. (2002): Increase at Jungfraujoch (CH) Ordonez et al. 2007: Mean Jungfraujoch, Zugspitze and Sonnblick et al Mean Zugspitze and


Concentrations of NOx at Kasernenhof ZÝrich (NABEL: Nationales Beobachtungsnetz fÝr Luftfremdstoffe, operated by EMPA)


Concentrations of organic compounds at compounds at Kasernenhof ZÝrich (NABEL: Nationales Beobachtungsnetz fÝr Luftfremdstoffe, EMPA) Luftfremdstoffe, EMPA)


Emission change in % 1990-1999 (EMEP, Vestreng et al., 2001)
NOx Switzerland Austria Germany Italy France - 36 - 12 - 39 - 23 - 18 VOC - 41 - 32 - 47 - 25 - 28


Time series of ozone monthly means for the UT (left panels) and the LS th LS (right panels) from MOZAIC Ozone-measurements. Ozone evolution similar (i) at many sites in northern at many sites in mid-latitudes (ii) ozone at high mountain sites (strong increase in the (strong in the second part of the 1990s)
Thouret et al., ACP 2006


7. Trends in North America
Ozone at National Park sites in USA ti it USA (Jaffee and Ray, 2007)


USA: S. Oltmans et al., 2004
300 - 200 Wallops Island (38N)
300 - 200 Boulder (40N)

500 - 300
Ozone Layer (hPa)

500 - 300

Ozone Layer (hPa)

700 - 500

700 - 500

850 - 700 1970-2003 Sfc - 850

850 - 700 1985-2003 Sfc - 850


Tarasick et al., 2005: 1980s: Resolute: 75oN;
Churchill:59oN; Goose Bay:53oN; Edmonton:53oN


Tarasick et al., 2005: 1990s, Resolute: 75oN; et al 75
Chruchill:59oN; Goose Bay:53oN; Edmonton:53oN; Alert: 82.5oN; Eureka: 80.1oN 80


8. Trends in Tropics
Lelieveld et al., Science 2004 li ld increase in ppb/y 1978-2003


Oltmans et al., 2006: Increase at Mauna Loa because of change in origin of air mass ii


9. Conclusions and open questions
· No reliable measurements of preindustrial (free fp (f tropospheric) ozone available increase War · Large increase from World War II to early 1990s (European measurements): Consistent with precursor emission increase · Late 1970s to late 1990s: Discrepance between ozone change from commercial air craft commercial air measurements (GASP/MOZAIC) and European ozone sondes.


Conclusions, open questions questions
- 1990s: North Canadian ozone sondes: Changes in th di Ch parallel with lower most stratospheric ozone changes - 1990s: Increase at UT: MOZAIC (North America, Atlantic, Europe) - Tropical trends: Increase strongly variable in space; role of changes in transport ? role of changes in transport - Southern hemisphere extratropics: very few data