Scientifc Advisory Groups Ozone UV GHG RG PC Aerosols GURME. CCLs. GAW Stations Global Regional Contributing. Empa. Programs IGBP SOLAS ileaps GMES

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1 Organization of GAW Expert Groups Chapter 2.3 OPAC-EPAC JSSC Empa Scientifc Advisory Groups Ozone UV GHG RG PC Aerosols GURME ET-WDC Administration Management Chapter 2.5 WMO/GAW Secretariat IGACO Offices Ozone/UV GHG Air Quality Aerosols Central Facilities Chapter 2.4 Empa QA/SACs WCCs RCCs NOAA CCLs WDCs & GAWSIS WOUDC WDCGG WDCA WRDC WDCPC WDC-RSAT NMHSs Observing Systems Chapter 3 Contributing Networks Empa GAW Stations Global Regional Contributing Satellites Aircraft Users & Applications Parties to the Conventions UNFCCC Vienna C. Systems GEOSS GCOS Programs IGBP SOLAS ileaps GMES Operational Centers Research Projects Empa christoph.zellweger@empa.ch 1

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7 Carbon Monoxide Trend at Jungfraujoch JFJ CO time series (one hourly data) from 1996 to The light blue curve represents a fitted baseline and the orange line the trend (after Thoning, et al., 1989, Novelli, et al., 1998; Novelli, et al., 2003) 21.3% carbon monoxide decrease from 1996 to 2007 at JFJ Corresponds to an annual decrease of 1.78% - or 2.66 ppb/year WCC-Empa GAW-CH Meeting

8 CO Emissions vs. Measurements Emission data from Yearly CO mixing ratios rel. to 1997 (Stations) / rel. CO emissions (Countries) BER HAE LAU LUG SIO ZUE JFJ HPB Year AT CH DE FR IT CO decrease mainly because of reduction of emissions Traffic influenced sites in Switzerland (BER, LAU) show strongest CO decrease Decrease at JFJ less pronounced, most likely due to influence of longrange transport Global scale events, e.g. enhanced biomass burning in 1998, is visible in JFJ data Laboratory for Air Pollution/Environmental Technology

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14 Mt.Kenya 14

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16 Bukit Koto Tabang O3 CO Deposition dominant during night Mixing in from troposphere during day Dilution with free tropospheric air during day 16

17 Benefit of WCC-Empa Audits Mt. Waliguan audits in 2000 / 2004 / 2009 (WCC-Empa and QA/SAC Switzerland) WCC-Empa audits and QA/SAC Switzerland guidance on data evaluation "rescued" valuable CO time series from Mt. Waliguan. Data was used in a publication (submitted to ACP) and can now be submitted to WDCGG. Zhang, F., et al, submitted to ACP We also used results from the WCC-Empa CO Audits in 2000 and 2004 at WLG to revise the WLG standards to the WMO2000 scale (Zellweger et al. 2000, 2004). In 2000, four cylinders from WCC were calibrated against working standards at WLG. Based on differences in the WLG and WCC results, a quadratic fit was applied to update values WCC-Empa GAW-CH Meeting

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23 Stability of the WCC-Empa WMO-2004 standard scale Ratio NIST, NMI, NPL / WMO NIST-SRM2612a-23-F-06 NIST-SRM2612a-23-F-32 NMI-PRM-8454E NPL-PRGM Year WMO-2004 scale at WCC-Empa is propagated using one standard (CA02854) Stability is monitored by inter-comparison against NIST / NMI / NPL standards Currently a potential change of % of CA02854 over the past few years can not be excluded christoph.zellweger@empa.ch 23

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26 WCC-Empa Audits at GAW stations 80 Alert 04 Ny Ålesund 97,01,05 Barrow 08 Pallas-Sodankylä 97,03,07 80 Polar Circle 40 0 Trinidad Head Mauna Loa 03 Samoa Mace Head 96,98,02,05,09 Arembepe 01 Hohenpeissenberg 97,06,(11) Zugspitze 96,97,01,06,(11) Jungfraujoch 40 99,06 Ryori 05 Mt. Waliguan Izaña 00,04,09 96,98,00,04,09 Assekrem Minamitorishima 03,07 Cape Verde (11) Mt Kenya 00,02,05,06,08,10 Bukit Koto Tabang 99,01,04,07,08,(11) Danum Valley Ushuaia 98,03,08 Cape Point 97,98,02,06,(11) Amsterdam Island 08 Cape Grim 02, Lauder / Baring Head 10 Neumayer Station South Pole O 3 /CO/CH 4 /CO 2 O 3 /CO/CH 4 O 3 /CO O 3 Not yet audited # Year(s) of audit(s)

27 Purpose of audits RCC Regional Calibration Centre Station Station CCL WCC World Calibration Centre Station Station Only one reference in the network Station Traceability chain as short as possible Regular audits lead to homogenous data series Station VV Abt WCC-Empa GAW-CH Conference

28 CO Audit Results Intercept (ppb) max. 10 ppb bias for range ppb max. 5 ppb bias max. 2 ppb bias GC with HgO reduction / UV detector 'RGA-3 type' Non-dispersive infrared monitor Vacuum UV resonance fluorescence monitor GC/FID/cat WMO-88 CO Scale Slope Plot of intercept versus slope for carbon monoxide audits conducted at Global GAW sites by WCC-Empa between 1997 and 2008 for different measurement techniques. The intercept / slope pairs are referenced against the WCC-Empa CO standard (calibrated traveling standard, WMO-2000 CO scale). The rhomboids displayed cover the range of slope-intercept combinations for a maximum of 2, 5, or 10 ppb bias for the concentration range ppb CO. WCC-Empa christoph.zellweger@empa.ch GAW-CH Meeting

29 CO Calibration Scales Conversions CSIRO assigned value (ppb) (CSIRO / SIO-1998 scale) CSIRO primary standard analyzed by WCC-Empa CSIRO surveillance standard analyzed by WCC-Empa WCC-Empa traveling standard analyzed by CSIRO slope = WMO-2000 (ppb) Residuals (ppb) Concentrations <= 189 ppb CO (WMO-88) WMO-2000 = * WMO * (WMO-88)^ e-06 * (WMO-88)^3 Concentrations > 189 ppb CO (WMO-88) WMO-2000 = * WMO-88 WMO-2000 (ppb) Concentrations below 195 ppb CO (WMO-2000 (years )) WMO-2000 = * WMO-2000 (00-03) * (WMO-2000 (00-03))^ e-07 * (WMO-2000 (00-03))^3 Concentrations above 195 ppb CO (WMO-2000 (00-03)) WMO-2000 = 1.00 * WMO-2000 (00-03) (no correction) Residuals (ppb) Residuals (ppb) WCC-Empa assigned value (ppb) (WMO-2000 scale) WMO-88 CO (ppb) WMO-2000 (years ) CO (ppb) CSIRO / SIO-1998 Linear conversion to WMO-2000 WMO-88 Non-linear conversion function to WMO-2000 WMO-2000 (before 2003) Non-linear conversion function to WMO-2000 for mole fractions <195 ppb WCC-Empa christoph.zellweger@empa.ch GAW-CH Meeting

30 CO audit results after scale conversion Intercept (ppb) max. 10 ppb bias for range ppb max. 5 ppb bias max. 2 ppb bias GC with HgO reduction / UV detector 'RGA-3 type' Non-dispersive infrared monitor Vacuum UV resonance fluorescence monitor GC/FID/cat Intercept (ppb) max. 10 ppb bias for range ppb max. 5 ppb bias max. 2 ppb bias GC with HgO reduction / UV detector 'RGA-3 type' Non-dispersive infrared monitor Vacuum UV resonance fluorescence monitor GC/FID/cat Slope Slope Plot of intercept versus slope for carbon monoxide audits conducted at Global GAW sites by WCC-Empa between 1997 and 2008 for different measurement techniques. The intercept / slope pairs are referenced against the WCC-Empa CO standard (calibrated traveling standard, WMO-2004 CO scale). The rhomboids displayed cover the range of slope-intercept combinations for a maximum of 2, 5, or 10 ppb bias for the concentration range ppb CO. WCC-Empa christoph.zellweger@empa.ch GAW-CH Meeting

31 CO audit results after scale conversion Intercept (ppb) max. 10 ppb bias for range ppb max. 5 ppb bias max. 2 ppb bias GC with HgO reduction / UV detector 'RGA-3 type' Non-dispersive infrared monitor Vacuum UV resonance fluorescence monitor GC/FID/cat Plot of intercept versus slope for carbon monoxide audits conducted at Global GAW sites by WCC-Empa between 1997 and 2008 for different measurement techniques. The intercept / slope pairs are referenced against the WCC-Empa CO standard (calibrated traveling standard, WMO-2004 CO scale). The rhomboids displayed cover the range of slope-intercept combinations for a maximum of 2, 5, or 10 ppb bias for the concentration range ppb CO. Slope WCC-Empa christoph.zellweger@empa.ch GAW-CH Meeting

32 Instrument development today CO MLO PAL ASK CVO CH 4 PAL +SF 6, N 2 O with ECD IZO RYO LAU +N 2 O, δ 13 C CO 2 CAWAS +H 2 O BAR PAL WLG Trend: from single to multi species analysis, from "slow" to "fast" measurements, from quasi-continuous to continuous measurements, from "chemical" to "spectroscopic" techniques. WCC-Empa GAW-CH Meeting Conference

33 Comparison CRDS vs. VURF CO instruments Hourly values agree to within 2 ppb except for periods with fast changes in the CO mixing ratio. Temporal coverage of VURF data slightly lower due to calibration every 2 nd hour (ca. 5 min). Only data < 1 ppm were considered due to linearity issues of the VURF instruments at higher mixing ratios. CO [ppm] Deviation to AL5001 [ppm] AL5001 G date [yy-mm-dd] Parallel measurements of VURF (Aerolaser AL5001) and 3 CRDS (Picarro G1302, G1302 and G2401) CO analyzers. 60-min averages are shown. WCC-Empa GAW-CH Meeting

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35 CO: ongoing & future activities gravimetric scale, regular up date continuous intercomparisons Ongoing audit programme Implementation of NRT Data submission (traceable / conversion to WMO scale & meta data) Foster 3rd dimension

36 7.3.2 Carbon Monoxide (CO) Task 7.54 Task 7.55 Task 7.56 Task 7.57 Task 7.58 Task 7.59 Task 7.60 Task 7.61 Task 7.62 [7.43] Provide a harmonized CO scale using improved instrumental techniques and intercomparisons. (SAG RG, CCL-NOAA, QA/SAC Switzerland, WCC-Empa 2008 ~ 2015) A new CO scale should be provided based on a new set of gravimetric standards (WMO-20XX scale). After consolidation, the CCL is expected to re-assign values for all cylinders including best estimates of the uncertainty. (CCL-NOAA, QA/SAC Switzerland, WCC 2012 ~ 2013) [7.47] Support surface sites interested in vertical profiling, with some flights coincident in time/space with satellite overpasses. (Secretariat, SAG RG 2012 ~ 2015) [7.46] Support civil aircraft based regular observations for the free troposphere. (Secretariat, SAG RG 2012 ~ 2015) Promote near-real-time transmission of data for carbon monoxide for modeling purposes. (SAG RG 2012 ~ 2015) [7.44] Develop an SOP detailing the necessary steps for the harmonization of CO time series currently archived at WDCGG, correct data accordingly, and request approval by the data submitters. (SAG RG, QA/SAC Switzerland, WCC, WDCGG 2012 ~ 2013) [7.48] Define requirements for combining satellite, aircraft and surface-based measurements. (SAG RG 2012 ~ 2015) Develop the methodology to accept and archive CO column data from satellite and ground based observations. (WDCGG, ET-WDC 2012 ~ 2015) Archive and develop integrated data sets using satellite, aircraft and surface-based measurements of CO. (WDCGG, SAG RG 2012 ~ 2015)