1. (Gas Chromatography Proton Transfer Reaction Time Of Flight) EGU talk 24.04.2012 1 GC-PTR-TOF Institute of Ionphysics and Applied Physics - University Innsbruck S. Langebner 1 *, C. Hasler 1, R. Schnitzhofer 1, I. Herdlinger-Blatt 1, F. Brilli 2, M. Jocher 3, and A. Hansel 1 1 Institute for Ion Physics and Applied Physics, University of Innsbruck, Austria; 2 IONICON Analytik GmbH, Innsbruck, Austria; 3 Agroscope ART, Federal Research Institute, Zurich, Switzerland; * stephan.langebner@uibk.ac.at ; X

2. 2 I. Introduction & Setup X

3. 3 Starting Point and Challenges  increased sensitivity:  real time measurements:  selectivity: ( SRI ) GC made a decisive contribution to the understanding of the atmospheric composition but can hardly track the dynamics of the atmospheric reactor… GC: PTR-TOF: PTR ‑ TOF [GRAUS 2010] allows to separate isobaric compounds (high mass resolution) and record whole mass spectra within a fraction of a second (fast duty cycle). Isomeric VOCs, however, still remain largely undistinguishable… X Based on the GC-FID-PTR-Quadrupole-MS idea (Davison et al., 2008): Combine the advantage of a GC (separation capability, sample preconcentration) and of an even more advanced PTR-TOF detector (with real time analysis, soft ionization, low LoD, fast duty cycle, isobaric separation). I.Intro II.Results III.Outlook

4. 4 Used GC and PTR-TOF X  GERSTEL "Online TDS G" consisting of - a "Thermo Desorption System" (TDS) - and a "Cold Injection System" (CIS), - with TENAX® TA  our PTR-TOF prototype  "HP 5890 Series 2 plus" GC  AGILENT column designed for the analysis of volatile priority pollutants  N 2 carriergas I.Intro II.Results III.Outlook

5. 5 Combined GC-PTR-TOF setup X direct PTR- TOF measurement GC-PTR- TOF measurement I.Intro II.Results III.Outlook

6. 6 Detailed Measurement Cycle  The 60min cycle starts with a 15min direct PTR-TOF measurement while TDS/CIS sampling takes place simultaneously followed by a 45min GC-PTR-TOF run. X I.Intro II.Results III.Outlook

7. 7 II. Results X

8. 8 Fragmentation of outside air  Retention times of protonated (PTR with H 3 O + ) compounds with abundance relative to their fragments as indicated by colors. X 101,097amu 83,086amu 510s516s 137,13amu 81,07amu fragmentation Ambient isomeric composition and isobaric information of fragmentation in the whole mass-range. I.Intro II.Results III.Outlook

9.  Comparison of a three day outside air monoterpene measurement with the blue line showing the ambient monoterpene concentration sum measured directly by PTR-TOF during TDS sampling. The colored bars show the separated monoterpene concentrations with the GC-PTR-TOF. 9 Continuous TOF vs. GC comparison I.Intro II.Results III.Outlook X

10. 10 III. Outlook & Summary X

11. 11 So have we achieved our goal?  Increased sensitivity:  Selectivity:  Real time measurements: GC-PTR-TOF:  Use micro packed columns for more flow requiring less dilution  Use a GERSTEL Modular Accelerated Column Heater (MACH GC) or specialized columns for faster programs X all this over -whole massrange with a high dutycycle, -quantitative, -at ambient concentrations, -selectivity for isomeric separation (sum formulas for fragments) I.Intro II.Results III.Outlook

12. 12 Acknowledgements  I want to show my sincere appreciation of the inspiring assistance and motivating cooperation by thanking all the diploma students, PhD students and postdocs of my group with the following quote: “Coming together is a beginning. Keeping together is progress. Working together is success.” [Henry FORD] and…  Markus JOCHER from ART Zürich  Dr. Jens HERBIG from Ionimed Analytic Ges.m.b.H. for the disussions and exchange after my presentations  GERSTEL Support  This research has received funding from the Austrian Science Fund (FWF): Project Number I655-B16.  “Förderungsstipendium der Universität Innsbruck, 2011”  This work was thoroughly presented 2011 in a seminar talk in Innsbruck at the Institute of Ionphysics and Applied Physics and presented as a Poster (A51A-0210) at the 2011 AGU Fall Meeting  publication is in preparation I.Intro II.Results III.Outlook X

13. 13 Questions Thank you for your attention! and… „Does anyone have any questions for my answers?“ [Henry KISSINGER] I.Intro II.Results III.Outlook X