Thermal Desorption Aerosol Gas Chromatograph Aerosol Mass Spectrometer (TAG AMS)

Transcription

1 AMS User Meeting - Milan 215 Thermal Desorption Aerosol Gas Chromatograph Aerosol Mass Spectrometer (TAG AMS) A. Bertrand N. Marchand

2 TAG - AMS Collaboration between Aerodyne Inc, Aerosol Dynamics and Berkeley First Aerodyne prototype sold to LCE (Aix-Marseile U.), and now one at Juelich

3 Introduction to the TAG - AMS Aerosol Mass Spectrometre (AMS) Quad Filter Thermal Desorption Aerosol Gas Chromatograh (TAG) AMS modified to accomodate a quad filter (for discrimation of lower m/z)

4 Introduction to the TAG - AMS Standards Injection System CTD Cell Fast Column Valveless Injection System Octal Temperature Controller

5 Kreisberg, AST, 211 Collection Thermal Desorption (CTD) Cell

6 Fast Column by VICI 15 min Run (4 C to 35 C) ~ 15 runs before it has to be changed

7 Heater Transfer Line

8 Transfer Line

9 Derivatization System Initial TAG modified to incorporate a DVZ system (Isaacman, AMT, 214)

10 Derivatization System Valveless Injection System Focusing Trap

11 Compounds Sucres Dérivés Syr. Et Gua. Stérols Autres Acides Mannosan Acide Palmitique Phenanthene Galactosan Acide Oleique Anthracene Levoglucosan Acide Palmitoleique Fluoranthrene Acide Stéarique Acephenanthrene Vaniline Acide Linoléique Pyrene Conyferyl Aldehyde Benzo[a]anthracene Syringaldehyde Di-ethyl phtalate Chrysene/Triphenylene Acide Vanilique Di-isobutyle phtalate Benzo[b,k]fluoranthrene Acetosyringone Di-butyl phatalate Benzo[i]fluoranthrene Benzyl-butyl phtalate Benzo[a,e]pyrene Cholesterol Bis(2-ethyl hexyl) phtalate Perylene Stigmasterol Indeno[1,2,3-cd]pyrene Acides Gras Phtalates B-Sistosterol BNT(2,1-d) Indeno[1,2,3-cd]fluoranthrene BNT(1,2-d) Dibenzoanthracene Acide DL glycérique BNT(2,3-d) Benzo(ghi)perylene Acide Abiétique Acide Pinonique Alcanes C18 à C36 Nor-Hopane (C29) HAP Souffrés HAP Hopanes Hopane (C3) Homohopane (C31) Secondary Biogenic Markers, Secondary Anthropogenic Marker (this list is non-exhaustive!!) Biomass Burning Other And Internal Standards Vehicular Biogenic Industrial Cooking D1 Adipic Acid D4 Phtalic Acid D31 Palmitic Acid D42 Eicosane D5Tetracosane D6 Cholesterol

12 Sequence

13 Sequence Injection standards internes 3 C Desorption

14 Sequence

15 Typical sequence includes : 3 min TAG sampling / AMS run 15 min desorption/dvz 15 min Chromatographic un Sequence

16 TAG User Interface User Interface developped by T. Hohaus Allow to build automatic sequence (control of valves, flow, heaters, AMS menu switching

17 TAG - AMS Signal Response Exploration and Integration Toolkit Peak Integration via TERN (TAG Exploration, Review, and integration) developped by D. Sueper and G. Isaacman Galactosan 2. Mannosa 3. Levoglucosan 4. Vanilic Acid 5. Phenanthrene 6. Anthracene Octadecane 8. Nonadecane 9. Palmitoleic Acid 1. Palmitic Acid 11. Eicosane 12. Oleic Acid Stearic Acid 14. Docosane 15. Tetracosane 16. Hexacosane 17. Octacosane Time (s)

18 Additional Toolkit TICC (TAG Inlab Concentration Calculator) et TACC (TAG Atmospheric Concentration Calculator) allow for quick access to concentration and timeseries, developed by A. Bertrand Need a discussion over calculation of PMF error matrix

19 TAG influence on AMS Pump AMS only Gas Load off TAG AMS He flow 1 psi TAG - AMS He flow 2 psi P P P P5 < P6 ~ Ionization efficiency with TAG and Quad Filter : 2,78E-8 Original AMS : IE 2E-7 Level of m/z of 18, 28, 32, 4 with TAG : 4 to 7 times those when no TAG is connected

20 TAG influence on AMS TAG AMS (Open Spectra) m/z Contamination peak from column bleeding and Transfer line 2 m/z 27 m/z AMS (Open Spectra) x Contamination persist for a while (at much lower level) even after TAG is disconnected

21 Thermodesorption : Levoglucosan TGA??? levoglucosan Unknown peak with similar ts than that of levoglucosan, at high level (not on filter) Possible thermal decomposition happening

22 TAG-AMS first deployment Arve Valley, in the Alps Passy station Alt : 583 m

23 TAG-AMS first deployment Gaseous Phase PTR-ToF-MS : Chemical composition and concentration of volatile compounds NO x, CO, CO 2, monitoring Particle Phase HR-ToF-AMS : Bulk chemical composition, concentration, and sizing of submicrometer non-refractory aerosol, PM 1 TAG-AMS : Hourly Organic Speciation, PM 1 MAAP : Measurement of Black Carbon, PM 1 SMPS, OPC : Aerosol size distribution and concentration SMPS ( nm) OPC (, um) AE 33 : Measurement of Black Carbon

24 Concentration (ug/m3) Total Organic (ug/m3) TAG-AMS first deployment 6 Organic Ammonium Sulfate Chrlorure Nitrate Black Carbon SMPS 4 3 sampling period 6 8 minutes each 6,7 l/min 2 12: AM 2/25/214 12: AM 2/26/214 12: AM 2/27/214 12: AM 2/28/ TAG Compounds (ng/m3) Vaniline Coriferyl aldehyde Syringalaldehyde Dérivés Syringuiliques Vanilic Acid Acetosyringone Palmitic Acid Linoleic Acid Oleic Acid Acides Gras Stearic Acid Abietic Acid Pinonic Acid Diethyl phtalate Dibutyl phtalate Phtalates Benzylbutyl phtalate Bis 2 ethyl hexyl phtalate Phenanthrene Anthracene Pyrene Benzo a anthracene Chyrsene n-octadecane n-nonadecane n-eicosane n-docosane n-tetracosane n-hexacosane Galactosan Manosan Levoglucosan HAP Alcanes Sucres Total Organic (AMS) 12: PM 2/25/214 12: AM 2/26/214 12: PM 12: AM 2/27/214 12: PM 12: AM 2/28/214

25 TAG Levoglucosan (ng/m3) TAG Levoglucosan (ng/m3) TAG-AMS first deployment TAG Levoglucosan AMS fragment C 2 H 4 O AMS C2H4O2+ (ug/m3). 12: PM 2/25/214 12: AM 2/26/214 12: PM 12: AM 2/27/214 12: PM 12: AM 2/28/ R 2 =.68 slope AMS C 2 H 4 O 2 (ng/m3)

26 Total Contribution Signal TAG-AMS first deployment x dat Concentration (ug/m3) /2/214 27/2/214 26

27 Conclusions Some issues, our instrument is the first operational instrument (still a prototype) Good sensitivity (5 to 1 times more sensitive than offline methods) Allows us to look at dynamic happening on very short time span (SOA formation and ageing of primary emissions) Thus, possibility to run experiments in smog chamber! Need to play on sampling time instead of dilution to avoid saturating the detector/column Questions over the thermostability of some molecules must be investigated more thoroughly Loss of sensitivity for AMS measurements Possible contamination

28 Introduction to the TAG - AMS