Updates on Aerodyne PAM Oxidation Flow Reactor. Andy Lambe 1

Transcription

1 ass Updates on Aerodyne PAM Oxidation Flow Reactor w at ere Andy Lambe 1

2 Potential Aerosol Mass (PAM) Oxidation Flow Reactor Developed by Bill Brune, improved and manufactured by Aerodyne Flow-through reactor, precursors exposed to O 3, OH, NO 3 ; HO 2, NO x Characterization: Kang et al., 27; Lambe et al., 211, 215; Bruns et al., 215 Modeling: Chen et al., 213; Li et al., 215; Peng et al., 215, 216 OVERVIEW 2

3 SOA formation from multi-generation oxidation of precursors OVERVIEW Lambe et al., 212 Chen et al., 213 Tkacik et al., 214 Ortega et al., 216 Palm et al., 216

4 Deliveries Serial # Delivery Institution 1 Dec 216 Washington University in St. Louis 2 Feb 216 Pacific Northwest National Laboratory 3 Feb 216 Desert Research Institute 4 Mar 216 Aerodyne 5 Jun 216 Chinese Academy of Sciences 6 Apr 216 Ohio State University 7 Jul 216 Hankuk University 8 Jul 216 Aerodyne 9 Jul 216 Peking University 1 Aug 216 Finnish Meteorological Institute 11 Sep 216 Laboratorie des Sciences du Climat et de l Environnement 12 Nov 216 National University of Singapore 13 Dec 216 University of California San Diego OVERVIEW 4

5 ales of days in the atmosphere utes in real time. l System Components Typical setup for measurements incorporating PAM reactor. Control software facilitates datalogging at 1 Hz and automated control with event sequencing for unattended operation (dashed Oxidation grey = analog flow input/output; reactor with dashed OFR185 red = digital and input/output) OFR254 capability O 3 chamber, Humidifier Autovalve, RH/T, Photodiode, User I/O Box, Flow Controllers APPLICATIONS E-box with ballasts and control board ADVANTAGES PAMControls software oratory or fied st udi es of secondar y aer osol Based on Penn State flo react or desi gn int roduc eration via gas-phase hydroxyl (OH) radical by Kang et al. (27) and further evaluated by La FIELD DEPLOYABLE zone (O 3 ) oxidation of gas-phase precursors. et al. (211). erogenous oxidation of primary aerosols. OVERVIEW Field deployable. 5

6 Unattended field operation in Mar 216 Gif-sur-Yvette, France OVERVIEW 6

7 OFR185 Dimming Voltage O 3 / ppm RSD (%) Irradiance RSD / uw cm -2 (%) 1 VDC 3.6 ± ± VDC 2.3 ± ± VDC 56.6 ± ± OVERVIEW 7

8 CMMCh Harvard Photochemical Chamber chamber vs PAM Hilkka Timonen, 4 th PAM Users Meeting 14 m 3 Teflonbag, with side 2.4 m 18 UVA 34nm lamps

9 CMMCh Harvard Photochemical Chamber chamber vs PAM Primary PAM Harvard High SOA/POA -ratio 2 Organics 15 µg m µg m Nitrate Sulfate Hilkka Timonen, 4 th PAM Users Meeting 4 µg m -3 3 Increase In BC Black carbon µg m : AM 2/4/215 12: PM 1: PM 2: PM 3: PM 4: PM 5: PM Date 9

10 OH oxidation with NO x O 3 + hn 254 O( 1 D) + O 2 O( 1 D) + H 2 O 2OH O( 1 D) + N 2 O 2NO N 2 O + hn 185 O( 1 D) + N 2 Lambe et al., in prep Peng et al., in prep NEW TECHNIQUES 1

11 Transition from RO 2 +HO 2 to RO 2 +NOdominant conditions: isoprene 1. Normalized Signal C 4-5 C 5 (NO 3 ) C 5 (NO 3 ) NO:HO 2 Lambe et al., in prep NEW TECHNIQUES 11

12 Transition from RO 2 +HO 2 to RO 2 +NOdominant conditions: a-pinene Lambe et al., in prep NEW TECHNIQUES 12

13 NO 3 radical generation O 3 + NO 2 NO 3 + O 2 NO 3 + NO 2 N 2 O 5 N 2 O 5 NO 3 + NO 2 NEW TECHNIQUES 13

14 a-pinene + NO 3 products detected with I-CIMS 8 (Clustered with I - ) Signal (Hz) C 1 H 15 NO 5 C 1 H 15 NO 4 C 1 H 15 NO 6 C 1 H 16 O 4 C 1 H 15 NO 7 C 7 H 9 NO 5 C 7 H 11 NO C 1 H 15 NO m/q NEW TECHNIQUES

15 SOA from limonene + NO3, detected with L-ToF-AMS 2 limonene + NO3 in PAM NO+NO2 CH2NO3 * 2 NO2 on (initiate N2O5, NO3 formation) 15 L-ToF-AMS Signal (Hz) Resid Open, Hz/ns 4 NO2 on 3 (initiate N2O5, NO3) 2 1 NO2 off NO2 on Closed, Hz/ns Diff, Hz/ns :3 PM 8/1/16 4: PM 4:3 PM 5: PM Date and Time CH 2 NO 3 C 6 H 4 C 3 H 8 O 2 C 5 O CS 2 13 CC5H3 13 CC2H7O K KCl CSO C S H CCH3 2 C N2 CHNO3 2 H SO O CCH3 C 43 SO 13 H 23 H CCH5 C 42 NN3 OH CCH7 36 NO O CC2 2 NH 29 O76.1 NO NEW TECHNIQUES

16 Outlook ~1 deliveries per year NO 3 radical to supplement OH radical (+ NO x ) Minor tweaks to hardware and software Synergistic applications with mass spectrometers 16