Thermal decomposition ionization and reaction detection Pump electronics HV electronics Calibration Box.

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Thermal decomposition ionization and reaction detection Pump electronics HV electronics Calibration Box

New PAN instrument: Chemical Ionization Mass Spectrometer based on Reaction of radicals with I - Fast Sensitive Selective Autonomous Slusher et al., JGR 2004

I - Chemistry I - reacts with N 2 O 5 and ClNO 3 –k = 1 x –product NO 3 - I- unreactive with PAN, HNO 3, HCl, SO 2, O 3, H 2 O, etc. Forms weak clusters with H 2 O, etc.

I - reactions with RO 2 I - + RO 2 → RO - + IO R = CF 3, CH 3 C(O), CH 3 CH 2 C(O), etc. i.e. RO - must be conjugated base of strong acid such as acetic acid used by Howard, Villalta, Froyd, deGouw, etc. to study kinetics of RO 2 + NO

CIMS Method Heated Inlet R-C(O)O 2 NO 2 → R-C(O)O 2 + NO 2 Detection I - + R-C(O)O 2 → RC(O)O - + IO Zero R-C(O)O 2 + NO → R-C(O)O + NO 2 or destroy PAN thermally before entering instrument

Then and Now Time resolution min sec Limit of detection2-3 pptv< 2 pptv/sec Sensitivity15-30 cps/pptv Background<200 cps # of PAN species48+ Instrument weight ~425 lbs~360 lbs (incl. Gases) (smaller Instr. coming) OperatorYes/NoNo!