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Implementing the monitoring requirements of VOCs - best practice in choice of methodology . C. Plass-Dülmer, Deutscher Wetterdienst, Hohenpeissenberg, D S. Reimann, Empa Dübendorf, CH N. Schmidbauer, NILU Kjeller, N. Some recent VOC stuff. D. Helmig et al. Ethane carpet from NOAA flasks
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Implementing the monitoring requirements of VOCs- best practice in choice of methodology C. Plass-Dülmer, Deutscher Wetterdienst, Hohenpeissenberg, D S. Reimann, Empa Dübendorf, CH N. Schmidbauer, NILU Kjeller, N
Some recent VOC stuff D. Helmig et al. Ethane carpet from NOAA flasks D. Helmig et al. Ln(propane/ethane) age of air mass at 5 high northern latitude sites C. Plass-Dülmer et al. NMHC at Central European Mountain Stations GAW – changing atmosphere, distribution and trends Major group of reduced gases –photochem., radicals, CO, O3, … Precursor for SOA formation – mass closures
The VOC-monitoring map of Europe WMO/GAW-VOC activity EMEP-VOC activity Data reporting Quality assurance Trend determination CCLs-WMO/GAW-VOC WCC-WMO/GAW AMOHA FP5 project
State of GAW-VOC programme CCL – agreement with NPL for NMHC, negotiations with NIST, VSL-NL, KRISS to take over responsibility for parts of CCL Scale hosted by CCLs WCC – station audits (GAW global stations and some central labs) WMO-VOC Expert Group meets biannually and works on expansion of measurement network, harmonisation, SOP, … Increasing number of data sets at WDCGG HOWEVER – problems with long-term commitment, network expansion, quality, …
The VOC-monitoring map of Europe WMO/GAW-VOC activity EMEP-VOC activity Data reporting Quality assurance Trend determination CCLs-WMO/GAW-VOC WCC-WMO/GAW ACTRIS-VOC Activities AMOHA FP5 project Integration/Harmonization Quality assurance SOPs Total VOC mass closure
ACTRIS Coordination of European VOC measurements NA4 - Trace gases networking: Volatile organic carbon and nitrogen oxides VOC definition: NMHCs (C2-C9 pure hydrocarbons) OVOCs (oxidised volatile organic compounds) terpenoides (biogenic hydrocarbons with a terpene-structure) Objectives • To integrate and harmonise VOC/NOy measurements in Europe • To implement standardised measurement protocols (SOPs) • To create a protocol for merging the information of ground-based in-situ and remote sensing capacities • To foster the dissemination of the methods and quality assured data
ACTRIS Coordination of European VOC measurements • GOALS • Development of SOPs within meetings of the European experts in the field • (link: GAW-VOC expert meetings/EMEP-VOC activity) • 2. Testing best measurement practices in experiments comprisinground-robin / on-site intercomparisons / station audits • (link: WCC-VOC) • 3. Merge ground-based in-situ measurements with vertical profile information.
ACTRIS Coordination of European VOC measurements • Task 1: Development of SOPs for harmonization of VOC-species measurements in Europe (EMPA, DWD, UHEL, NILU, JRC, CNRS) • Workshop-1 (EMPA) • data quality objectives (DQOs) • error assessment • data processing • QC criteria for the data delivery • Draft documents for SOPs • Plan station audits/round-robin exercises • Build on knowledge from recent projects (NOMHICE, AMOHA, and ACCENT), GAW expert group for VOC and the EMEP community (NILU) • Workshop-2 (EMPA) • final standardised operating procedures (SOPs) • Supply SOPs to serve the scientific community, GAW and EMEP
ACTRIS Coordination of European VOC measurements • Task 2 Testing best measurement practices in QA experiments for VOCs (EMPA, DWD, UHEL, NILU, JRC, CNRS) • Round-Robin exercises for synthetic standards • real-air reference-gases • sent to all scientific groups in Europe engaged in long-term VOC measurements • Real Air Reference Gases • special stainless steel cylinders • reference concentrations will be determined by EMPA, WCC-VOC, and DWD • In-situ Intercomparison measurement campaigns • NMHC at Jungfraujoch (Empa) • OVOC at Finokalia (FORTH) • Audits at selected sites will be performed by the WCC-VOC. • Report on Round Robin Results • Report on Intercomparison Results • Results used for final version of the SOP
ACTRIS Coordination of European VOC measurements Task 4.1.3 Link vertical profile information for VOCs to ground based measurements (BIRA-IASB, DWD, NILU, CSIC) MAXDOAS FTIR Comparison with on-line ground based measurements (WS-1 and WS-2) Document on the results (BIRA-IASB)
Task 3.1 Development of OVOC instrumentation for mass-closure experiments (EMPA, DWD) • Development of on-line GC-technique for standardised use in GAW • (water-trap, enrichment (cooled adsorbent trap), capillary column, FID or MS) • standardized sampling, enrichment and thermal desorption module • Attachable to any GC-FID system • Test against PTRMS as a reference system • Recommend for use in GAW • Use knowledge from existing OVOC systems (EMPA, DWD, NCAR, UoY, …) • Task 3.2 Performance of mass closure at different sites (field campaigns)
ACTRIS – Time Table Start of ACTRIS Workshop-1 Drafts for standardised operating procedures (SOPs) for VOC measurements Results of Round Robin exercise of VOC mixtures Results of VOC side-by-side inter-comparison exercise of ambient air and test gases Results of station audits for VOCs (WCC-VOC) Workshop-2 Final SOPs for VOC measurements Link between surface and column information of VOC Recommendation on sustainability of VOC measurements in Europe Report on standardized OVOC instrument based on developed GCMS technology Delivery of OVOC data to EBAS data centre 03/11 11/11 03/12 03/13 11/13 11/13 03/14 09/14 12/14 03/15 03/12 09/14
The VOC-monitoring map of Europe WMO/GAW-VOC activity EMEP-VOC activity Data reporting Quality assurance Trend determination CCLs-WMO/GAW-VOC WCC-WMO/GAW ACTRIS-VOC Activities AMOHA FP5 project Integration/Harmonization Quality assurance SOPs Total VOC mass closure
Conclusions 8 mountain station data sets – first steps towards climatology Mixing ratios and hydrocarbon patterns at < 1205m (5 sites) very similar Declining concentrations with altitude Neg. trends of 2 % /yr for C2-C3 alkanes (+/- 1%) 3-6 % /yr for C4-C7 alkanes (+/- 2%) 2-3 % /yr for C2-C3 alkynes and ethene (+/- 2%) 4 % /yr for propene and benzene (+/- 2%) 5-10 %/yr for toluene and xylenes (+/-3-5%)