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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..