Paper ID Number 17371

Abstract Number 316

Section: ENVR Air Monitoring

H2O2 and CH3OOH measurements in DC3 using multi-reagent ion CIMS

A. S. McNeilla, V. A. Treadawaya, B. G. Heikesa, I. K. C. Silwalb, D. W. OSullivanb
(a) University of Rhode Island, (b) United States Naval Academy

Motivation

Key Findings
A. PCIMS instrument sampled successfully from the surface to approx. 40 kft on 22 research
flights, flown in central and eastern United States.

Why H2O2 and CH3OOH?

Important for understanding atmospheric
oxidation pathways (C)
Differences in aqueous solubility allow
for tracing air masses through convection (B)
Why develop this new CIMS method for peroxides? (A)
Much faster sampling for airborne application
Improved sensitivity and range of detection
Specificity
Flight-worthiness
Reagent ions employed are green
Potential for detection of other analytes

B. Sampling was successfully conducted on 12 days in deep convection - 4.5 days in OK/TX,
7.5 days in CO an example of which is shown below in Observations Near Convection.
Increase in mixing ratio of CH3OOH at outflow indicates transport from below.
Absence of H2O2 at outflow suggests precipitation scavenge during vertical transport.

Figure 1 Schematic of the vertical

cross-section of a squall line with processes
critical to chemical species ingestion
(http://www2.acd.ucar.edu/dc3)

C. Convective outflow was sampled on 8 days east of the Kansas, an example of which is
shown below in Observations - Downwind.
Decrease in CH3OOH is consistent with photochemical theory; however, a portion of this
decrease could also be attributed to mixing.
Increase of H2O2 with time is consistent with photochemical theory and unlikely to have
been caused by mixing surrounding air is suspected to contain less H2O2. However,
mixing cannot be ruled out because of high H2O2 signals observed during ascent.

B. Observations Near Convection

A. Instrument

C. Observations - Downwind

DC8 peroxide data

courtesy of J. Crounse (H2O2)
and J. St. Clair (CH3OOH),
California Institute of Technology

ascent

Figure 2 Instrument schematic

Peroxide Chemical Ionization Mass Spectrometer

Figure 3 RF17 peroxide

measurements near convection
(above) and 3-D flight track (below)

Reagent gas: ultrapure air + 400 ppm CO2

Reagent ions: O2-, CO2O2 Ion Chemistry:

Species

m/z

O2-H2O2

66

O2-CH3OOH

80

CO2O2-H2O2

110

Water Ligand Exchange improves m/z 66 signal,

reduces m/z 80 and 110 signals
Calibration: in-field microfluidics, post-mission
coil and microfluidics, blank Carulite-200 trap

Acknowledgements

Figure 4 RF16 Legrangian outflow

photochemistry of peroxides
(above) and flight track (below)

We would like to thank NSF Atmospheric Chemistry for support, the NCAR Research Aviation Facility for the use of the Gulfstream-V,
the DC3 Science Team, including the scientific steering committee (Mary Barth, Chris Cantrell, and others; http://www2.acd.ucar.edu/dc3/science-team).