Ari Laaksonen, Jukka Rukkainen: University of Kopio, FI. Highly time resolved measurements of inorganic gases and aerosols during the EMEP intensive campaigns 2006/07 Eiko Nemitz, Rick Thomas, Chiara di Marco, Gavin Phillips: Centre for Ecology and Hydrology (CEH) Edinburgh, UK. Rami Alfarra, Andre Prevost, Urs Baltensperger: Paul Scherrer Institute, CH. Rene Otjes, Jan Willem Erisman: Energy Centre of the Netherlands (ECN), Petten, NL. Gerald Spindler: Institute for Tropospheric Research (IFT), Leipzig, DE. Ari Laaksonen, Jukka Rukkainen: University of Kopio, FI.

EMEP Intensive Measurement Periods June 2006 / January 2007 New feature of the new measurement strategy Also provide an interim solution until EMEP Supersites (Level 2 & 3) are established Periods for June 2006 & January 2007 focussed on the gas / aerosol partitioning of inorganic aerosol Measurements include Daily measurements with manual techniques (Wenche) Hourly measurements with two different continuous techniques (this presentation) So far only preliminary data available from continuous online techniques (except Cabauw  presentation by Rene Otjes)

The Aerodyne Aerosol Mass Spectrometer Quantitative measurement Concentration & size distribution But, limitations: Measurement of sub-micron aerosol (100% across 40-600 nm) Thermal vapourisation at 550°C: non-refractory aerosol only Good for: NH4NO3, (NH4)2SO4, NH4Cl, organic aerosol Does not measure: sea salt, crustal material Ionisation: Thermal vapourisation, followed by electron impact ionisation (70 eV) Less fragmentation than laser ionisation More fragmentation than chemical ionisation

Thermal Vaporization & Electron Impact Ionization Aerodyne Aerosol Mass Spectrometer (AMS) Particle Particle Beam Aerodynamic Sizing Composition Generation Quadrupole Mass Spectrometer Chopper Thermal Vaporization & Electron Impact Ionization TOF Region Aerodynamic Lens (2 Torr) Quantitative information of chemical composition and size distributions of volatile and semi-volatile aerosols. Aerodynamic lens, EI , QMS.. Particle Inlet (1 atm) Turbo Pump Turbo Pump Turbo Pump 100% transmission (30-600 nm), aerodynamic sizing, linear mass signal. Development of an Aerosol Mass Spectrometer for Size and Composition Analysis of Sub-micron Particles. Jayne et al., Aerosol Science and Technology 33:1-2(49-70), 2000.

The ECN MARGA/GRAEGOR Continuous wet denuder (NH3, HNO3, HCl, SO2, HONO) Steam jet aerosol collector (NH4+, NO3-, SO42-, Cl-) (MARGA also Na+, K+, Ca2+, Mg2+) Anions: online anion IC Cations: online cation IC (MARGA) diffusion membrane / conductivity for NH4+ (GRAEGOR) Two separate sampling boxes for PM2.5 and PM10 (GRAEGOR TSP)  More information in presentation by Rene Otjes

The MARGA/GRAEGOR

Comparison AMS vs. MARGA MARGA/ GRAEGOR Gases No Yes (NH3, HNO3, HCl, SO2,HNO2) Transmission 40 – 600 nm (~PM1) PM2.5 & PM10/TSP Sizing Yes Aerosol fraction Non-refractory only: NH4+, NO3-, SO42-, Cl-, OM, H2O Total: NH4+, NO3-, SO42-, Cl- (MARGA only: Na+, K+, Ca2+, Mg2+)

1st EMEP Intensive Measurement Period June 2006: Gas / aerosol partitioning of inorganic aerosol (contributions: ECN, NL; Univ. Kopio, FI; PSI, CH) Cabauw, The Netherlands Auchencorth, Scotland Total PM2.5 = > 12.4 mg m-3 Total PM1 = 8.6 mg m-3 Mace Head, Ireland Melpitz, Germany Total PM1 = 6.0 mg m-3 Payerne, Switzerland Total PM1 = 19.4 mg m-3 Harwell, England Total PM2.5 = 13.7 mg m-3

Total Measured Concentrations June 2006

Total Measured Concentrations Jan 2007

Overview of Average Concentrations: June 2006

Overview of Average Concentrations: January 2007

Comparison of the two Intensive Periods

June 2006: Nitrate

June 2006: Sulphate

June 2006: Ammonium

June 2006: NH3 & SO2

June 2006: HNO3 & HCl

June 2006: HNO3 & HONO

Diurnal Cycles January 2007 June 2006

Diurnal Cycles: Gases June 2006: solid line January 2007: dotted line

Concentration Products [NH3] x [HNO3]

Size distribution at CEH EMEP campaign Scottish Site

Average size distributions Auchencorth Payerne Mace Head

Charge Balance (NH4+ vs. sum of NO3- and SO42-)

Contribution of Regional Ammonium Aerosols to Exceedances of PM10 Air Quality Standards in Urban Areas

The AMS can distinguish at least two types of organic aerosol Hydrocarbon like organic aerosol (HOA) Freshly emitted particles High alkane and alkene contribution Looks like lubricating oil Proxy for ‘primary organic aerosol (POA)’ Oxygenated organic aerosol (OOA) High in O (measured as m/z 44 = CO2+) Looks like fulvic acid Proxy for ‘secondary organic aerosol (SOA)’

The organic aerosol fraction Thanks a lot for giving this Presentation!

Behaviour of HOA & OOA (Auchencorth, June 2006)

Data Uses The EMEP intensive measurements provide a powerful dataset. Model evaluation. Joint EMEP / ACCENT activity on intercomparison of CTMs? (Combine with daily measurements.) Bulk concentration Gas / aerosol partitioning Fine vs. coarse nitrate Size distributions Diurnal cycles Primary vs. secondary organic aerosol Synthesising analysis and publication (EMEP report & peer-reviewed). Data towards aerosol climatology for Europe Analysis in local context

Was the approach successful? Successful given that this is a new modus operandi, although more sites would be preferable Gap in Southern and Eastern Europe Conflict between long-term research commitments of the participating institutes More gaps in data (due to instrumentation) than daily measurements

Planning of Future Campaigns If we want to get more universities & research institutes involved: Plan much further in advance & do not change dates (should be planning 2008 campaigns now) Avoid periods close to Christmas / New Year Improve the communication channels Arrange for instruments to be taken to Eastern and Southern Europe (difficulties with lobbying & funding) ACCENT/BIAFLUX funds available to take instrumentation to other countries (order €30k) Possible topics: More extensive measurements of hourly concentrations of gases and aerosols (too late for 2007; would need to be 2008) Speciation of organic compounds (incl. biomass burning marker 14C) Aerosol physics (particle size distribution, number, hygroscopicity, volatility etc.)

Availability of ground-based AMS Instruments Centre for Ecology & Hydrology, UK (1 + 1 on order) University of Manchester, UK (2) University of Kopio, FI (1) University of Helsinki, FI (1) Paul Scherrer Institute, CH (1) Institute for Tropospheric Research, DE (1) University of Augsburg, DE (1) Jülich, DE (1) Max Planck Institute for Chemistry, Mainz, DE (2?) Total: > 12  Discussion at AMS User Group Meeting October in Reno

Concentration Statistics