Feister and Warmbt (1987), Long-term measurements of surface ozone in - PowerPoint PPT Presentation

TOAR-Observations: How well do we know global long-term tropospheric ozone changes? Co Co-ch chairs: s: David Tarasick and Ian Galbally Co Co-aut ut ho hors: Owen Cooper, Martin Schultz Timothy Wallington, Johannes Stähelin, Gerard Ancellet, Thierry Leblanc, Jerry Ziemke, Xiong Liu, Martin Steinbacher, Corinne Vigouroux, James Hannigan, Omaira García, Gilles Foret, Prodromos Zanis, Elizabeth Weatherhead, Irina Petropavlovskikh, Helen Worden, Mohammed Osman, Jane Liu, Meiyun Lin, Maria Granados- Muñoz, Anne M. Thompson, Samuel J. Oltmans, Juan Cuesta, Gaëlle Dufour, Valerie Thouret, Birgit Hassler, Thomas Trickl Also so: The many scientists whose careful observations over 170 years inform this work GMD Meeting – 23/05/2018 - 1

Feister and Warmbt (1987), Long-term measurements of surface ozone in the German Democratic Republic, J. Atmos. Chem. 5 , 1–22. GMD Meeting – 23/05/2018 - 2

Bojkov (1984), from a paper at the QOS GMD Meeting – 23/05/2018 - 3

Schönbein (1840), On the odour accompanying electricity and on the probability of its dependency on the presence of a new substance, Philos. Mag., 17 , 293-294. Schönbein named it "ozone", from the Greek ozein meaning "to smell". Schönbein (1845) developed a method using KI and starch-impregnated paper strips. When exposed to ozone the reaction O 3 + 2KI + H 2 O → O 2 + I 2 + 2KOH releases iodine, which forms a blue-coloured complex with the starch. Comparing to a standard colour scale gave a semi-quantitative ozone measurement. • Interest in ozone was very high, in part because of its suggested role as an “air purifier” and in eliminating disease organisms, particularly cholera ( Fox, 1873). Christian Friedrich • Measurements were made at hundreds of sites in Schönbein (1799– Europe, the Americas, Australia, Asia, Africa and 1868) Antarctica. GMD Meeting – 23/05/2018 - 4

Albert-Lévy (1877) developed a quantitative method, bubbling air through a solution of KI and arsenite, with subsequent titration. The measurements were made until about 1910. Volz and Kley (1988) reproduced the apparatus of Albert-Lévy and showed that it was accurate. They also analyzed the Montsouris data and showed that it averaged about 11 ppbv. • The method was not very sensitive; measurements took 24 hours. The interest was again public health. • Other routine measurements of air and water chemistry were also made, including ammonia, as well as sulphate and nitric acid in rainwater. GMD Meeting – 23/05/2018 - 5

Schönbein paper measurements calibrated to Montsouris data Marenco et al. (1994), Evidence of a Long-term Increase in Tropospheric ozone from Pic du Midi Data Series: Consequences: Positive Radiative Forcing, J. Geophys. Res., 99 , 16617-16632. GMD Meeting – 23/05/2018 - 6

Note that these curves 80% RH are not inconsistent Kley et al. (1988): chamber calibrations of Schönbein papers. Colour development response to time peaks and then reverses. N.B. Exposure times were 12-24 hours Kley et al. (1988) “ The Schönbein data are too qualitative in nature to serve as historic ozone reference data .” GMD Meeting – 23/05/2018 - 7

The Montsouris Observatory ozone measurements 1876–1910  24-hour averages; biased low relative to daytime measurements  Paris in 1900 was a city of 2.5 million people, with coal supplying most of the city’s energy needs. From records of coal use Ionescu et al. (2012) estimate SO 2 levels of 55 ppbv  Measurements of sulphate in rainwater, also made at Montsouris, range from 3.5-37.0 mg l -1 SO 3 ( Albert-Lévy, 1907; 1908). The average of 13.9 mg l -1 corresponds to ~25-75 ppbv of SO 2  Ionescu et al. (2012) estimate 28 ppbv for the average NO 2 concentration in 1905 (from coal)  Other measurements at the Observatory find on average 12 ppbv of nitrogen oxides (measured as nitric acid)  80,000 horses and 5,700 dairy cattle in Paris generated large amounts of NH 3 ; an average of 28 ppbv is reported ( Albert-Lévy, 1903)  Municipal Observatory location, at the edge of a major city, was urban or suburban, not representative of background atmosphere.  Hartley , 1881: “ It is impossible, therefore, to accept the figures given in the Annuaire de L’Observatoire de Montsouris as indicating anything like the true proportion of ozone usually present in country air … ” GMD Meeting – 23/05/2018 - 8

Other early measurements About 8-10 long path UV measurements from the 1930s  Modern standard uses Hearn (1961); some older  measurements used Fabry and Buisson (1931), Läuchli (1928), Ny and Choong (1933) or Vigroux (1953) and need to be adjusted by up to 11% ~50 other measurements use one of several KI techniques  Wavelength (nm) 253.65 289.36 296.73 302.15 334.15 Fabry and Buisson (1931) 1.046E-17 1.964E-18 7.541E-19 3.730E-19 5.847E-21 Läuchli (1928) 1.275E-17 n/a 5.914E-19 n/a 5.999E-21 Ny and Choong (1933) 1.222E-17 1.851E-18 7.019E-19 3.188E-19 5.742E-21 Vigroux (1953) 1.065E-17 1.560E-18 5.854E-19 2.820E-19 4.971E-21 Inn & Tanaka (1953) 1.141E-17 1.466E-18 5.759E-19 2.845E-19 5.228E-21 Hearn (1961) 1.148E-17 1.474E-18 5.973E-19 2.863E-19 4.268E-21 GMD Meeting – 23/05/2018 - <#>

Northern Temperate (Europe): Historical surface ozone measurements UV measurements KI measurements 60 TOAR database: 45-50 ο N, 5-10 ο E, 5yr, day Mean ozone (nmol mol -1 ) 50 40 30 20 10 Modern average = 32 ppbv, 39% more than the historical average of 23 ppbv 0 1900 1910 1920 1930 1940 1950 1960 1970 1980 1990 2000 2010 Year GMD Meeting – 23/05/2018 - 10

Historical free tropospheric ozone balloon UV measurements 60 Regener and Regener, 1934 O'Brien et al., 1936 Regener (1938) Mean 0-10 km ozone column (DU) 50 Coblentz and Stair, 1939; 1941 Paetzold (1955a,b) Modern range (min-max) for 45-50 o N, 5-10 o E 40 Uncertainty? 30 20 10 Increase of ~17% (± 20%) 0 1900 1910 1920 1930 1940 1950 1960 1970 1980 1990 2000 2010 Year Historical UV measurements of free tropospheric ozone. The modern range shown is that of maximum and minimum monthly average values, from ozonesondes, for the period 1990-2012. GMD Meeting – 23/05/2018 - 11

When related to the UV Bias ECC sondes - Upper Troposphere - UV referenced 40 photometer measurements, Weighted mean = 5.3 ± 5.2% 30 the results indicate a 1-5% 20 high bias in the troposphere, 10 with an uncertainty of 5%, Bias (%) 0 but no evidence of a change -10 with time. Barnes et al. (1985) Hilsenrath et al. (1986) -20 Beekman et al. (1995) Bias ECC sondes - Lower Troposphere - UV referenced Reid et al.,1996 40 Smit and Kley (1998) -30 Smit and Sträter (2000) Weighted mean = 1.1 ± 4.9% Deshler et al. (2008) 30 -40 1960 1965 1970 1975 1980 1985 1990 1995 2000 2005 2010 2015 20 Year After ≈1995, for EN -Sci with 1% 10 Bias (%) KI add 4-8% positive bias in LT; 0 2-6% in UT -10 Torres & Bandy (1978) -20 Barnes et al. (1985) Hilsenrath et al. (1986) Reid et al.,1996 Smit and Kley (1998) -30 Smit and Sträter (2000) Deshler et al. (2008) -40 1960 1965 1970 1975 1980 1985 1990 1995 2000 2005 2010 2015 GMD Meeting – 23/05/2018 - 12 Year

Bias BM sondes - Upper Troposphere - adjusted to UV reference 30 BM sonde 20 tropospheric 10 response has 0 Bias (%) changed with -10 time Attmannspacher and Dütsch (1970) -20 Attmannspacher and Dütsch (1980) Hilsenrath et al. (1986) Lehmann (2005) -30 Bias BM sondes - Lower Troposphere - adjusted to UV reference Beekman et al. (1994) 30 Kerr et al. (1994) Beekman et al. (1995) -40 Smit and Kley (1998) De Backer et al. (1998) 20 Stübi et al. (2008) -50 1960 1965 1970 1975 1980 1985 1990 1995 2000 2005 2010 2015 10 Year 0 Bias (%) -10 -20 Attmannspacher and Dütsch (1970) Attmannspacher and Dütsch (1980) Hilsenrath et al. (1986) -30 Lehmann (2005) Beekman et al. (1994) Kerr et al. (1994) -40 Smit and Kley (1998) De Backer et al. (1998) Stübi et al. (2008) -50 1960 1965 1970 1975 1980 1985 1990 1995 2000 2005 2010 2015 AGU2017: ARQD Sem inar – 02/ 2017: A21Q GMD Meeting – 23/05/2018 - <#> 21Q-03 CRD Seminar – 2/11/2017 - 13 03 – 12/ 02/ 01/ 12/ 12/ 01/ 2018 12/ 2017 2018 - 13 2017 - 13 13 13 Year

Satellite measurements - Upper tropospheric bias CCD (Ziemke et al. 2005) TOR (Fishman et al. 2003) 20 GOME (Liu et al. 2005) TRAJ (Schoeberl et al. 2007) TES (Nassar et al. 2008) OMI-MLS (Ziemke et al. 2006) 10 OMI(Prof) (Ziemke et al. 2014) IASI (Boynard et al. 2009) Bias (%) TES (Boxe et al. 2010) IASI (Dufour et al. 2012) 0 IASI+GOME2 (Cuesta et al. 2013) OMI+TES (Fu et al. 2013) GOME2 (Miles et al. 2015) IASI (Boynard et al. 2016) -10 OMI(Prof) (Huang et al. 2017) -20 1980 1985 1990 1995 2000 2005 2010 2015 Year Published evaluations are in general single averages over a short period of time. Biases are fairly modest, but standard deviations are large. GMD Meeting – 23/05/2018 - 14