1. 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.

2. 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)

3. The Aerodyne Aerosol Mass Spectrometer
Quantitative measurement
Concentration & size distribution
But, limitations:
Measurement of sub-micron aerosol (100% across 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

4. 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 ( 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.

5. 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

6. The MARGA/GRAEGOR

7. 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+)

8. 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

9. Total Measured Concentrations June 2006

10. Total Measured Concentrations Jan 2007

11. Overview of Average Concentrations: June 2006

12. Overview of Average Concentrations: January 2007

13. Comparison of the two Intensive Periods

14. June 2006: Nitrate

15. June 2006: Sulphate

16. June 2006: Ammonium

17. June 2006: NH3 & SO2

18. June 2006: HNO3 & HCl

19. June 2006: HNO3 & HONO

20. Diurnal Cycles
January June 2006

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

22. Concentration Products [NH3] x [HNO3]

23. Size distribution at CEH EMEP campaign Scottish Site

24. Average size distributions
Auchencorth
Payerne
Mace Head

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

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

27. 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)’

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

29. Behaviour of HOA & OOA (Auchencorth, June 2006)

30. 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

31. 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

32. 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.)

33. 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

35. Concentration Statistics