Rebecca Hornbrook1,*, Eric Apel1, Dan Riemer2, Alan Hills1, Greg Huey3, Dan O’Sullivan4,

Don Blake5, Armin Wisthaler6, Paul Wennberg7, and the DC3 Science Team

1Atmospheric Chemistry Division, NCAR, Boulder, CO, *rsh@ucar.edu; 2 University of Miami 3 Georgia Institute of Technology, 4 United States Naval Academy, 5 University of California – Irvine, 6University of Innsbruck, 7California Institute of Technology

Trace Organic Gas Analyzer (TOGA) Case Study 1: 29-May, Oklahoma Convection • Fast online GC/MS VOC measurement

• Up to 53 different VOCs • High sensitivity: detection limits of NMHCs &

OVOCs to ppt, many halocarbons to sub-ppt • 35-s integrated measurements every 2 min • Altitude independent 0 - 50,000 feet

Fig. 1. Simplified schematic of the TOGA.

NMHC OVOCs HVOCsi-butane formaldehyde CH3Cl

n-butane acetaldehyde CH2Cl2

i-pentane propanal CHCl3

n-pentane butanal CCl4

2-methylpentane pentanal CH3Br

n-hexane 2-pentanone CH2Br2

n-heptane acrolein CHBr3

propene methacrolein CHBr2Cl

i-butene methanol CH2ClI

1,2-butadiene ethanol CH2I2

isoprene acetone

a-pinene methyl ethyl ketone (MEK)

b-pinene methyl t-butyl ether (MTBE)

camphene methyl vinyl kentone (MVK)

limonene

benzene Othertoluene HCN

ethylbenzene+m-/p-xylene CH3CN

o-xylene dimethyl sulfide (DMS)

2-methyl-3-butene-2-ol (MBO)

DC3 Targeted Compounds

GC Oven

16x103

12

8

4

0

altitu

de

, m

20:00 21:00 22:00 23:00 00:00 01:00

29-May-12 RF06, UTC

600

500

400

300

200

100

0

ME

K,

pp

tv

4000

3000

2000

1000

0

n-b

uta

ne

, p

ptv

42

40

38

36

34

32

30

La

titud

e, °N

GV altitude Latitude MEK n-butane

4000

3000

2000

1000

0

n-b

uta

ne

, p

ptv

20:005/29

20:30 21:00 21:30 22:00 22:30 23:00 23:30 00:005/30

00:30

DC-8, 29-May-12

14

12

10

8

6

4

2

0

Altitu

de

, km

42

40

38

36

34

32

30

La

titud

e, °N

DC-8 Altitude Latitude n-butane (WAS)

Case Study 2: 22-June, Colorado Convection + High Park fire 2000

1500

1000

500

0

n-b

uta

ne

, p

ptv

20:006/22

21:00 22:00 23:00 00:006/23

01:00 02:00

DC-8, 22-June-12

14

12

10

8

6

4

2

0

Altitu

de

, km

42

41

40

39

38

37

36

La

titud

e, °N

50x10-3

40

30

20

10

0

CH

3C

N,

pp

bv

DC-8 Altitude Latitude n-butane (WAS) CH3CN (PTR-MS)

400

350

300

250

200

150

100

CH

3C

N,

pp

tv

23:30 00:00 00:30 01:00 01:30 02:00

22-Jun-12 RF17, UTC

250

200

150

100

50

0

n-b

uta

ne

, pp

tv

16x103

12

8

4

0

altitu

de

, m

1200

1000

800

600

400

200

HC

N, p

ptv

100

80

60

40

20

0

Acro

lein

, p

ptv

43

42

41

40

39

38

La

titu

de

GV Altitude Latitude acrolein (TOGA) CH3CN (TOGA)

HCN (TOGA) n-butane (TOGA)

1

10

100

1000

[VO

C],

pp

tv

CH

2O

CH

3C

HO

acro

lein

pro

pa

na

l

buta

nal

ace

ton

e

ME

K

me

tha

no

l

eth

an

ol

2.0

1.5

1.0

0.5

0.0([V

OC

]/[n-C

4 ])o

utflo

w/([V

OC

]/[n-C

4 ])in

flow

[VOC] inflow (GV) [VOC] outflow (GV) [VOC] inflow (DC8) [VOC] outflow (DC8) [VOC] ratio (GV) [VOC] ratio (DC8)

1

10

100

1000

[VO

C], p

ptv

pro

pane

n-b

uta

ne

i-buta

ne

n-p

en

tane

i-penta

ne

n-h

exa

ne

n-h

ep

tane

pro

pene

1,3

-buta

die

ne

benzene

tolu

ene

C8-a

rom

atics

2.0

1.5

1.0

0.5

0.0

([VO

C]/[n

-C4 ])

ou

tflow/([V

OC

]/[n-C

4 ])in

flow

1

10

100

1000

[VO

C], p

ptv

HC

N

CH

3C

N

DM

S

HN

O3

H2O

2

MH

P

CH

2B

r2

CH

Br3

isopre

ne

MV

K+

meth

acro

lein

a-p

inen

e

3.0

2.5

2.0

1.5

1.0

0.5

0.0

([VO

C]/[n

-C4 ])

ou

tflow/([V

OC

]/[n-C

4 ])in

flow

16x103

12

8

4

0

altitu

de

, m

20:00 21:00 22:00 23:00 00:00 01:00 02:00

22-Jun-12 RF17, UTC

400

350

300

250

200

150

100

CH

3C

N,

pp

tv

400

300

200

100

0

Bu

tan

e,

pp

tv

43

42

41

40

39

38

37

36

La

titud

e, °N

GV altitude Latitude CH3CN (TOGA)

n-butane (TOGA)

Fig. 2. GV (yellow) and DC-8 (mauve) flight tracks. Fig. 3. Time series for n-butane from DC-8 (left) and GV (right) flights. Inflow periods and outflow

periods were determined using elevated butane.

Fig. 4. Plots of average inflow and outflow mixing ratios for a number

of observed species. (bars), and ratios of species to

n-butane in outflow vs. inflow.

Fig. 5. Above, GV (cyan) and DC-8 (pink) flight tracks, and (right) smoke entrained Into convection from High Park fire. Installed on the GV

Fig. 6. Time series for n-butane and CH3CN from DC-8 (above) and GV (right) flights. Inflow periods and outflow periods were

determined using elevated butane from two convection events between 22:00 and 23:00 (a), and between 23:30 and 02:00, (b)

with and (c) without elevated fire-tracer acrolein.

0.1

1

10

100

1000

[VO

C], p

ptv

CH

2O

CH

3C

HO

acro

lein

pro

panal

bu

tan

al

aceto

ne

ME

K

meth

an

ol

eth

an

ol

2.0

1.5

1.0

0.5

0.0

([VO

C]/[n

-C4 ])

ou

tflow/([V

OC

]/[n-C

4 ])in

flow

0.1

1

10

100

1000

[VO

C],

pp

tv

pro

pa

ne

n-b

uta

ne

i-b

uta

ne

n-p

en

tan

e

i-penta

ne

n-h

exa

ne

n-h

ep

tan

e

pro

pe

ne

1,3

-bu

tad

ien

e

be

nze

ne

tolu

en

e

C8

-aro

ma

tics

4

3

2

1

0

([VO

C]/[n

-C4 ])

ou

tflow/([V

OC

]/[n-C

4 ])in

flow

0.1

1

10

100

1000

[VO

C],

pp

tv

HC

N

CH

3C

N

DM

S

HN

O3

H2

O2

MH

P

CH

2B

r2

CH

Br3

iso

pre

ne

MV

K+

meth

acro

lein

a-p

ine

ne

3.0

2.5

2.0

1.5

1.0

0.5

0.0

([VO

C]/[n

-C4 ])

ou

tflow/([V

OC

]/[n-C

4 ])in

flow

[VOC] DC-8 inflow [VOC] DC-8 outflow DC-8 ratio [VOC] GV inflow [VOC] GV outflow (a) GV ratio (a) [VOC] GV outflow (b) GV ratio (b) [VOC] GV outflow (c) GV ratio (c)

Fig. 7. Plots of average inflow and

outflow mixing ratios for a number

of observed species. (bars), and ratios of

species to n-butane in

outflows vs. inflow.