1. ISSAOS 2008 l‘Aquila, September 2008 Aerosol Mass Spectrometry: General Principles and examples Hugh Coe School of Earth, Atmospheric and Environmental Sciences University of Manchester Reading: D Murphy, The design of single particle laser mass spectrometers, in: Mass Spectrometry Reviews, 2007, 26, 150-165. M. R. Canagaratna et al., Chemical and microphysical characterisation of ambient aerosols with the Aerodyne Aerosol Mass Spectrometer in: Mass Spectrometry Reviews, 2007, 26, 185-222. H. Coe and J. D. Allan, “Aerosol Mass Spectrometry” in “Atmospheric techniques” ed D. E. Heard, Blackwell Scientific Publishing, 2006 http://cires.colorado.edu/jimenez/ams-papers.html thanks to Jose Jimenez for the slides showing component parts of aerosol mass spectrometers

2. I.General Introduction – the advantages of Aerosol Mass Spectrometry II.The component parts of an aerosol mass spectrometer III.Examples of different mass spectrometric methods IV.Advantages and disadvantages of different mass spectrometric methods General Outline

3. I.General Introduction – the advantages of Aerosol Mass Spectrometry II.The component parts of an aerosol mass spectrometer III.Examples of different mass spectrometric methods IV.Advantages and disadvantages of different mass spectrometric methods General Outline

7. I.General Introduction – the advantages of Aerosol Mass Spectrometry II.The component parts of an aerosol mass spectrometer III.Examples of different mass spectrometric methods IV.Advantages and disadvantages of different mass spectrometric methods General Outline

8. thanks to Jose Jimenez for the slides showing component parts of aerosol mass spectrometers

9. Aerosol Inlets Need to entrain aerosols from the atmosphere into a vacuum Aerosol Inlets Need to entrain aerosols from the atmosphere into a vacuum Need to concentrate particles and remove the gas 2.5 x 10 19 molecules cm -3 in ambient air 3.2 µg m -3 of particulate S = 10 -7 moles m -3 of S 6.2x10 23 x10 -7 x10 -6 =6.2x10 10 molecules cm -3 or around 2 ppb Aerosol Inlets Need to entrain aerosols from the atmosphere into a vacuum Need to concentrate particles and remove the gas 2.5 x 10 19 molecules cm -3 in ambient air 3.2 µg m -3 of particulate S = 10 -7 moles m -3 of S 6.2x10 23 x10 -7 x10 -6 =6.2x10 10 molecules cm -3 or around 2 ppb May need to introduce a size dependent velocity onto the particles

13. Effects on beam width non spherical particles may affect the ability of particle lens systems to focus the particle beam

19. Vaporization Desorption/ionisation process can be coupled together - This is certainly simpler but it is very difficult to quantify the mass of material detected A two step process of desorption followed subsequently by ionisation provides a way of more easily quantifying mass However, this comes at a price - More volatile species may decompose - Refractory material (NaCl, dust, soot) will not evapourate unless the temperature is very high Vaporisation may be performed by -Thermal methods or -IR laser absorption

20. Ionization Ideally should: Produce ions from either solid or liquid particles or the desorbed gas Need to produce a high number of ions per molecule (high efficiency) Ideally the number of ions produced is proportional to the number of molecules The ionisation is selective and universal The molecular fragmentation is reproducible

22. Laser Desorption/Ionisation: The LDI process on particles is poorly understood Laser wavelength is important Sulphuric acid hard to ionise – due to transparency in UV Dependent on laser beam cross sectional intensity Laser pulse width dependence In larger particles, not all particle may be ionized Laser power density -lower fluence reduces fragmentation -higher fluence allows improved ionisation

27. Ion Trap Can do MS n Can investigate ion- molecule reactions

28. I.General Introduction – the advantages of Aerosol Mass Spectrometry II.The component parts of an aerosol mass spectrometer III.Examples of different mass spectrometric methods IV.Advantages and disadvantages of different mass spectrometric methods General Outline

32. I.General Introduction – the advantages of Aerosol Mass Spectrometry II.The component parts of an aerosol mass spectrometer III.Examples of different mass spectrometric methods IV.Advantages and disadvantages of different mass spectrometric methods General Outline

33. Advantages/Disadvantages of laser and thermal systems: laser based systems:thermal systems: -can ionise a wide range of- Can be used to deliver species quantitative mass information -deliver single particle info- deliver information on the and so enable estimates of particle ensemble mixing state -do not have consistent - Can be traced back to ionisation and suffer shot to well characterised ionisation shot variability libraries

34. Example: PALMS (Murphy et al NOAA)

35. Murphy, D.M., Thomson, D.S. & Mahoney, T.M.J. (1998b) In situ measurements of organics, meteoritic material, mercury, and other elements in aerosols at 5 to 19 kilometers, Science, 282 (5394), 1664–1669.

36. Example : Dall’Osto et al (Birmingham) ATOFMS Identification of Hydroxymethanesulphonate during urban fog processing event ART-2a analysis based on a neural network algorithm was used to identify a number of different particle classes REPARTEE experiment in central London

37. Example: Dall’Osto et al (Birmingham) ATOFMS Identification of Hydroxymethanesulphonate during urban fog processing event

38. Example: Jim Smith (NCAR) Thermal Desorption Ionisation Chemical-Ionisation MS (TDICIMS) chemical analysis of ultrafine particles

39. Example: Jim Smith (NCAR) Thermal Desorption Ionisation Chemical-Ionisation MS (TDICIMS) chemical analysis of ultrafine particles

40. Example: Jim Smith (NCAR) Thermal Desorption Ionisation Chemical-Ionisation MS (TDICIMS) chemical analysis of ultrafine particles

41. Example: Jim Smith (NCAR) Thermal Desorption Ionisation Chemical-Ionisation MS (TDICIMS) chemical analysis of ultrafine particles

42. Example: Jim Smith (NCAR) Thermal Desorption Ionisation Chemical-Ionisation MS (TDICIMS) chemical analysis of ultrafine particles