1. Analysis of polar organic compouds in size resolved aerosol by Py-GC-MS and derivatisation GC-MS András Hoffer Max Planck Institute for Chemistry Mainz In cooperation with András Gelencsér, Marianne Blazsó

2. Objectives Identification and quantitative determination of polar organic compounds in aerosol extracts by derivatisation GC-MS (Mainz) - from all filter samples (including backup) - from MOUDI samples for the most abundant compounds Method has been established but speciation to be supported by GC chemical ionisation MS and GC- HRMS on selected samples (Hungary) Direct structural characterisation of bulk organic aerosol by on-line derivatisation Py-GC-MS (Hungary) - qualitative but yields information on HULIS / polyacids as well - relative ratios of pyrolysis products may be used for source apportionment (see Blazsó et al. JAAP)

3. Derivatisation Py-GC-MS methodology - pyrolysis: flash, 400°C, 20s - derivatisation reagents: TMAH 10  l, TBAH, BSTFA - GC column: HP5MS 0.32 x 30 m 0.25  m - temperature program: 50°C 1 min - 10°C/min 300°C hold 5min - identification: Wiley 275 spectrum library - sample need: spot of 0.3 cm 2 Instrumentation: Pyroprobe 2000 GC Agilent 6890 / MS 5973 (EI) (quadrupole)

4. Py-GC-MS with TMAH

5. Identified compounds 43 (39) compounds tentatively identified Major compound classes: - Monocarboxylic including fatty acids -(C 6 -C 28 ) - most abundant n-C 16 - few unsaturated compounds (C 18:1 ) - Dicarboxylic acids -(butanedioic acid, pentanedioic acid, methyl-butanedioic acid, 2-butenedioic acid) - Aromatic compounds di-, tri- hydroxy benzene and benzoic acids and/or methoxybenzoic acids and derivatives (TBAH derivatisation required)

6. - Anhydrosugars/sugars (levoglucosan) - n-alkanes(C 23 -C 28 ) The relative amount of the aromatic compounds to the levoglucosan are higher (1.3 - 5) in the burning period compare to the transition period Some aromatic compounds (coumaryl compound) are missing from the transition period sample burning p eriod transition period C/G=1.09 S/G=0.65S/G=0.9 grass and softwood origin hardwood burning

7. Py-GC-MS with BSTFA

8. - Similar compound classes were identified as in the TMAH-treated sample. - The identified aromatic compounds where the same as in previous mesurements made with water extraction. - The relative amount of the aromatic compounds is higher in the burning period (1.4-5.5). Hydrolysis of high MW compounds  mostly methoxy guaiacyl syringyl units can be identified (compare to Graham et al.) several aromatic hydroxy compounds in aqueous extract Identified compounds Derivatisation with TBAH

9. Instrumentation: GC Fisons 8000 / MS Trio 1000 (EI, quadrupol) - GC column: SPB5 0.32mm x 30 m 0.25  m - temperature program: 50°C 1 min  10°C/min 300°C hold 5min - sample need: ~ 6cm2 Sample preparation - Extract in ACN (6cm 3, 1h) - Derivatised with PFBHA (O-(2,3,4,5,6-pentafluorobenzyl) hydroxy amine after drying with BSTFA GC-MS measurements

10. Ion fragments EI : m/z=73, 75 [Si(CH 3 ) 3 ] +, [OH=Si(CH 3 ) 2 ] ·+ relative intensity: (20-100%) m/z =117 [COOSi(CH 3 ) 3 ] ·+ monocarboxylic acids relative intensity: 61-97% (except aromatic carboxylic acids) and strong M-15 as well m/z= 147 [(CH 3 ) 2 Si=OSi(CH 3 ) 3 ] ·+ 2 active H-atoms relative intensity: ~100% m/z= 181 [C 6 F 6 CH 2 ] + carbonyl groups relative intensity 50-100% /Yu et al. 1998/

12. 181 147 117

13. - Identification of individual compound is underway - The identified compounds will be confirmed by standards - Quantification will be performed in SIM with internal standard method - Identification of individual compounds: end of March - Quantitative analysis: end of August - Data evaluation and writing papers: September - Planned time schedule of the work