toga/ fast gas chromatograph mass spectrometer (fgcms

TOGA/ Fast Gas Chromatograph Mass Spectrometer (FGCMS) – prototype for HIAPER

Gas chromatograph/Mass Spectrometer

Measurement campaigns

TRACE-PIDEASMIRAGEINTEX-BARCTASOASISMIRAGE-Shanghai

Eric ApelAlan HillsDan Riemer, U. MiamiRich Lueb

• High sensitivity VOCs/OVOCs to ppt

• High selectivity 2-D GC/MS

• Rapid 2 minutes

• Altitude independent 0-50,000 feet

• semi – Autonomous

Trace Organic Gas Analyzer (TOGA)

Gulfstream G-V

Steve GabbardRoger HendershotRudy Montoya

Eric ApelAlan HillsRebecca HornbrookDan Riemer

LN2 dewar

electronics box

CAG

pump box

MS

traps

10-L Cryogenic LN2 dewar

TOGA compounds (may do a subset or switch subsets on the fly)

Hydrocarbons

Propane Isoprene1-Butene t-2-Pentenei-Butene c-2-PenteneButane i-Pentanei-Butane o-XyleneBenzene m/p-XyleneToluene 1,3,5-TrimethylbenzeneEthyl Benzene 1,2,4-Trimethylbenzenet-2-Butene -Pinenec-2-Butene -PinenePentane Camphene1,3-Butadiene MyrceneLimonene

Formaldehyde

Oxygenates

Acetaldehyde MethanolPropanal EthanolButanal AcetonePentanal ButanoneMethacrolein 2-PentanoneMethyl Vinyl Ketone 3-PentanoneMethyl Butenol Methyl t-Butyl Ether

Halocarbons

Chloroform (CHCl3) Tetrachloromethane (CCl4) dibromomethane

Methylene chloride (CH2Cl2) CFC-113 diodomethane

Methyl chloride (CH3Cl) HCFC-141b bromocjhloromethane

Methyl bromide (CH3Br) HCFC-134a bromoiodomethane

Tetrachloroethane (CH2Cl4) 1,2-Dichloroethane (C2H4Cl2) chloroiodomethane

Tetrachloroethylene (C2Cl4) Methyl Iodide (CH3I)

Bromoform iodoform

Nitrogen and sulfur compounds

AcetonitrileDimethyl Sulfide (DMS)

DMSO?

300

250

200

150

100

50

0

VO

C,

pp

tv

14

12

10

8

6

4

2

0

Altitu

de

, km

Butane

30

25

20

15

10

5

0

VO

C,

pp

tv

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

Flight Time, UTC

14

12

10

8

6

4

2

0

Altitu

de

, km

Toluene

14

12

10

8

6

4

2

0

Altitu

de

, km

100

80

60

40

20

0

VO

C,

pp

tv

CH2Cl2

CH3Cl/10

CCl4

CHCl3

14

12

10

8

6

4

2

0

Altitu

de

, km

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

Flight Time, UTC

300

250

200

150

100

50

0

VO

C,

pp

tv

Acetonitrile

60

50

40

30

20

10

0

VO

C,

pp

tv

14

12

10

8

6

4

2

0

Altitu

de

, km

Benzene

14

12

10

8

6

4

2

0

Altitu

de

, km

1500

1000

500

0

VO

C,

pp

tv

Acetone

TOGA flight data, 6 May 2011

Calibration curve for the TOGA low concentration formaldehyde study. Five measurements were obtained for each data point using formaldehyde standards introduced to TOGA. The standards were generated using the permeation system described in Figure 2 coupled to the dilution apparatus described in Figure 4.

Formaldehyde low concentration study

HCHO pptv

0 100 200 300 400 500 600 700

Ion

Cou

nts

0

5000

10000

15000

20000

25000

TOGA Formaldehyde Lab Data

Retention time

0.1 0.2 0.3 0.4 0.5

Ion

Cou

nts

0

500

1000

1500

2000

2500

3000

590 pptv

343 pptv

195 pptv

zero

Signal-to-noise (S/N) of 195 peak = 35LOD for 5 x S/N = 195* 5/35 = 28 pptv, but because the peak we use for the S/N calculation contains some background, the peak used for the S/N calculation is actually~ 2x larger than it should be relative to the noise so the detection limit at 5x is closer to 50-60 pptv.

DMSMSA

ARCTAS-CARB

x

ISOMVKMACR

CH3CHOMEKButane

CH3CNAcetoneMeOH

All species depleted in MBL

TRACE Organic Gas Analyzer – TOGA – VOC measurements INTEX-BRole of Ocean in Global Atmospheric Budgets

Oxygenates: acetone, methanol CO

Median Values – TOGA

MOZARTAcetone -4.7 um m2 day-1

Methanol-3.3 um m2 day-1

Organic

microlayer

Physical uptake limited by both gas –

and aqueous –phase transfer

Sea salt spray

ROLE OF OCEAN IN ATMOSPHERIC

BUDGETS OF OVOCs

SINK?

hυ

Organic microlayer

hυ

VOCs

OCEAN

MBL

Ftop = V * ΔC

FMBL = prod - loss

Focean = -Fmbl-Ftop

Singh et al., 2003, D. Riemer, I. Faloona, private correspondence

Previous Work:

Methanol, Acetone, etc.. – large ocean source – Nature Singh et al, 2001

– small ocean sink (Singh et al, 2003)

Acetone: Marandino et al (Saltzman (2005)) – Fluxes of Acetone

- large ocean sink

- Gradient fluxes of ~ -3 -12 um m2 day-1 (Eddy Co-variance)

Preliminary results (back of envelope) here:

Flux (Assume MBLL – MBLP = 0)

Acetone -5.5 um m2 day-1 (Saltztman - ~ - 9 um m2 day-1 )

Methanol-8.32 um m2 day-1

CH3CN ran out of time this morning..

Preliminary results w/ losses:

Flux (without boundary layer loss but not production)

Acetone -4.7 um m2 day-1

Methanol-3.3 um m2 day-1

CH3CN ran out of time this morning..