Harrison Yates

University of Notre Dame
Mentor: Steven R. Schill
PI: Dr. Timothy H. Bertram
! Very important oxidizing agent
! Atmospheric lifetime on order
of milliseconds
! Direct atmospheric
measurement is difficult
! Common reactions:
! OH + CO ! CO
2
+ H
! CH
4
+ OH ! CH
3
+ H
2
O
5: Gas Phase Radial Chemistry in
the Troposphere, Monks, 2004
5
! C
3
H
6
O + hv ! CH
3
+ CH
3
CO
! CH
3
+ O
2
! CH
3
O
2
! CH
3
O
2
+ HO
2
! CH
3
OOH + O
2
! CH
3
OOH + hv ! CH
3
O + OH
1

! O
3
+ hv ! O(
1
D) + O
2
! Two options:
! O(
1
D) + O
2
! O
3
! O(
1
D) + H
2
O ! 2 OH
2

Acetone Ozone
! Want to compare formation rates:
1
Photolysis of Atmospheric Ozone in the
Ultraviolet Region, Yutaka Matsumi, Masahiro
Kawasaki, 2003
2
Atmospheric Chemistry and
Physics, John Seinfeld, 2006

Sinks
Sources
! Industrial processes
! Plant-derived emissions
! Oxidation of hydrocarbons
! 22 day half-life
! Direct human health effects
! OH photolysis not widely studied
! Photolysis (64%)
! OH reaction (24%)
! Surface Deposition (12%)
! Predicts photolysis rates in the atmosphere
! Challenge is solving for rate constant (k) values
! Input parameters to solve for k values
3

! k is a function of:
! Time of day
! Location
! Altitude
! Properties of the compound
3
http://cprm.acd.ucar.edu/Models/TUV/
! miniCIMS malfunction was motivation to only use
one flight
! Creates ion beam
! IMR chamber (benzene)
! Two octopoles
! Quadrupole mass analyzer
! SIMION software for ion trajectory simulation
! Model with working octopole
IMR Chamber Octopole 1 Octopole 2 Quadrupole Mass Analyzer
Benzene Flow
D
e
t
e
c
t
o
r

S
a
m
p
l
e

A
i
r

F
l
o
w

! Model with malfunctioning octopole
! Result: ion beam scattering and weaker signal
IMR Chamber Octopole 1 Octopole 2 Quadrupole Mass Analyzer
Benzene Flow
S
a
m
p
l
e

A
i
r

F
l
o
w

D
e
t
e
c
t
o
r

! Highest levels over Sierra Nevadas
! Past studies have ranged from 0.36 to 2.31 PPBV
4

4
Acetone in the Atmosphere: Distribution, Sources,
and Sinks, H. B. Singh, D. O’hara, D. Herlth, D. R.
Blake, J. D. Bradshaw, M. Kanakidau, P. J. Crutzen,
1994
! Areas of interest show overall high ozone levels
! Acetone is important in tropospheric OH formation when present
! Order of magnitude: 10
5
-10
6

Sierra Nevadas Santa Barbara Channel
! Order of magnitude: 10
9

! Past studies indicate 40% of OH is from ozone photolysis
5

5
Gas Phase Radial Chemistry in the
Troposphere, Monks, 2004
Sierra Nevadas Santa Barbara Channel
! Mean ratio of 135.7 (compare to previous study with a ratio of 17.3)
5

! Acetone plays a small, but important role in OH production
5: Gas Phase Radial Chemistry in
the Troposphere, Monks, 2004
! Mean ratio of 3562 when acetone photolysis observed
! Acetone’s role in OH production is nearly negligible in the area
! First airborne miniCIMS campaign to provide a working data set
! Atmospheric acetone is a small, but not negligible OH source
! Ozone/acetone spanned three orders of magnitude
! Ozone was found to be a significantly larger contributor
! Overall project results are similar to past OH photolysis studies
5

5
Gas Phase Radial Chemistry in the
Troposphere, Monks, 2004
! Dr. Timothy H. Bertram
! Dr. Barry Lefer
! David Manura
! Dr. Emily Schaller
! Rick Shetter
! Steven R. Schill
! Dr. Matthew Zoerb
! The Bertram Group
! NASA SARP 2014

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