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Materials Sci ence & Technolog y The Value of On-site Comparisons During WCC Audits for Methane, Carbon Dioxide and Carbon Monoxide Christoph Zellweger 1 , Juha Hatakka 2 , Martin Steinbacher 1 , and Brigitte Buchmann 1 1 Empa, Laboratory for

  1. Materials Sci ence & Technolog y The Value of On-site Comparisons During WCC Audits for Methane, Carbon Dioxide and Carbon Monoxide Christoph Zellweger 1 , Juha Hatakka 2 , Martin Steinbacher 1 , and Brigitte Buchmann 1 1 Empa, Laboratory for Air Pollution/Environmental Technology, Duebendorf, Switzerland 2 FMI, Finnish Meteorological Institute, Helsinki, Finland ESRL Global Monitoring Annual Conference, Boulder CO, USA

  2. World Calibration Centre WCC-Empa Established 1996 for Surface Ozone  1997: Carbon Monoxide  2000: Methane  2007: Collaboration with WCC-N 2 O  2010: Carbon Dioxide  Since 2011, parallel  measurements with traveling instrument (CO, CH 4 , CO 2 ) 2 WCC-Empa – NOAA ESRL Global Monitoring Annual Conference, May 2012

  3. History of parallel measurements during audits GGMT Meeting Jena 2009: It was recognized that audits using  travelling standards provide only limited information in some cases, and parallel measurements with a travelling instrument would be desirable. GGMT Meeting Wellington 2011:  WCC-Empa showed first results from a comparison made at Cape Point, and the following recommendation was made: ‘The World Calibration Centre for CO 2 , CH 4 , and CO (EMPA) has demonstrated the benefits of using a travelling instrument for GAW station audits. It is very desirable that the air intake is included in the testing process. This practice is encouraged whenever possible’. 3 WCC-Empa – NOAA ESRL Global Monitoring Annual Conference, May 2012

  4. What have we learnt from the first comparison? 410 Parallel measurements using a  WCC-Empa (Picarro G2401) CPT (URAS-4) completely independent setup 400 CO2 [ppm] (inlet, instrument, calibration) 390 provide very valuable additional 380 information on the performance of a measurement system. 10 CPT - WCC [ppm] 5 It is of utmost importance to use an  0 independent inlet system, but -5 addtional measurements with the -10 travelling instrument using the 11-03-17 11-04-06 11-04-26 11-05-16 station inlet system provide further ° 1.3 ° useful information. Picarro G2401 ° ° ° ° ° ° ° ° ° ° ° ° ° 1.2 ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° The Picarro G2401 fully suitable as ° ° ° °  ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° (CO)wet/(CO)dry ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° 1.1 ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° a travelling instrument for on-site ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° 1.0 ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° audits (CO 2 and CH 4 ), but ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° 0.9 ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° improvement of water vapor ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° 0.8 ° CO (ppb) correction is needed (CO). ° ° ° ° Dilution only 56 Experimental data 115 ° 0.7 Fit 172 0.0 0.5 1.0 1.5 2.0 2.5 3.0 H2O mixing ratio (%) 4 4 WCC-Empa – NOAA ESRL Global Monitoring Annual Conference, May 2012

  5. Audit Pallas Audit by WCC-Empa (April 2012) Station is equipped with analyzers of the newest generation.  Agreement between PAL and WCC-Empa was good.   An audit using travelling standards was made. Results see below. In addition, the audit includes parallel measurements of CO,  CO 2 and CH 4 which are currently still ongoing. 12-04-18 07:04:00) to 12-04-18 14:01 Picarro G2401 CFKADS-2018 12-04-18 07:04:00) to 12-04-18 14:01 Picarro G2401 #2012 12-04-18 06:58:30) to 12-04-18 13:55 Picarro G2401 CFKADS-2018 4 CO 2 Picarro CH 4 CO Picarro 0.4 4 CO2 - <WMO-X2007> (ppm) [CO - <WMO-2000>] (ppb) [CH4 - <NOAA04>] (ppb) 2 0.2 2 0.0 0 0 -0.2 -2 -2 -0.4 -4 -4 1700 1800 1900 2000 2100 0 100 200 300 400 0 50 100 150 200 <NOAA04> (ppb) <WMO-X2007> (ppm) <WMO-2000> (ppb) Unbiased ozone = OA - 0.11 (ppb) / 0.983 TEI49i #619917500 12-04-18 17:57:00) to 12-04-18 17:57 Licor LI7000 12-04-17 09:43:30) to 12-04-18 10:58 PeakPerformer 1 #084 10 0.4 20 O 3 Analyzer CO 2 Licor Sufficient CO PP1 0.3 15 CO2 - <WMO-X2007> (ppm) 5 [CO - <WMO-2000>] (ppb) Good [OA - SRP] (ppb) 0.2 10 0.1 0 5 0.0 Good -5 -0.1 0 Sufficient -0.2 -10 -5 340 350 360 370 380 390 400 0 50 100 150 200 0 20 40 60 80 100 120 <WMO-X2007> (ppm) <WMO-2000> (ppb) SRP (ppb) 5 WCC-Empa – GAW-CH Meeting 2012-05-16

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