trace gases measurements from the global hawk whole air sampler during the airborne tropical...
TRANSCRIPT
1
Trace gases measurements from the Global Hawk Whole Air Sampler during
the Airborne Tropical Tropopause Experiment 2013 (ATTREX-2)
Maria Navarro1, E. Atlas1, R. Lueb1, R. Hendershot2, S. Gabbard2, X. Zhu1, L. Pope1
1) Division of Marine and Atmospheric Chemistry, Rosenstiel School of Marine and Atmospheric Science, University of Miami, Miami, Florida, USA
2) Atmospheric Chemistry Division, National Center for Atmospheric Research, Boulder, Colorado, USA
with data from MMS and NOAA O3 groups
2
OBJECTIVES
• Characterize variability and distribution of organic trace gases in the UT/LS
• Evaluate the chemical gradients in the TTL
• Evaluate the budget and partitioning of organic bromine
• Examine source signatures and input of natural vs. anthropogenic trace species in the tropical UT
3
GWAS on ATTREX-2
RF01
RF03
RF04
RF05
RF06
Altit
ude
(m)
UTC (sec)
388 samples 45 vertical profiles
RF01RF03RF04RF05RF06
4
ATTREX-2 TRACE GAS SPECIES FROM GWAS
Chlorofluorocarbons Yrs SCFC-11 50 ACFC-12 102 ACFC-113 85 A
HalonsHalon 1211 20 AHalon 2402 20 A
Hydrochlorofluoroarbons/ HydrofluorocarbonsHCFC_141b 9.4 AHCFC-22 13 AHCFC_142b 19.5 A
Solvent Carbon Tetrachloride 40 AMethyl chloroform 4.8 A
OtherCarbonyl Sulfide (COS) 30 N/A/BMethyl Chloride 1.5 N/B
Solvents Yrs SMethylene Chloride 0.3 AChloroform 0.4 A/NTetrachloroethylene 0.3 ATrichloroethylene 0.02 A
Methyl HalidesBromoform 0.1 NMethyl Bromide 0.8 A/N/BMethylene Bromide 0.4 NMethyl Iodide 0.01 NCHxBryClz 0.1 N
Organic nitratesMethyl nitrate 0.08 A/NEthyl nitrate 0.04 A/NPropyl nitrate 0.03 A/N
Non- Methane Halocarbons Ethane (C2H6) 0.2 AEthyne 0.06 A/BPropane 0.04 ABenzene 0.04 A/B
Others1,2 dichloro ethane 0.3 AChlorobenzene 0.05 A
Longer Lived Species Shorter Lived Species Shorter Lived Species
SourcesA= antropogenic/industrialN= natural/marineB=Biomass burning
5
AREA OF ANALYSIS
27.0
18.3
LAT (deg)
ALT
(Km
)
6
VERTICAL CHEMICAL GRADIENTS LONGER LIVED SPECIES
420
400
380
360
The
ta (
K)
600560520480CFC-12 (pmol/mol)
420
400
380
360
The
ta (
K)
300280260240220200180160CFC-11 (pmol/mol)420
400
380
360
Thet
a (K
)
90858075706560CFC-113 (pmol/mol)
420
400
380
360
The
ta (
K)
5.04.54.03.53.02.5Halon 1211 (pmol/mol)420
400
380
360
The
ta (
K)
3028262422201816HCFC 141b (pmol/mol)
420
400
380
360
The
ta (
K)
11010090807060CCl4 (pmol/mol)
Bins of 10K θ
4% 2%
2% 7%
4%6%
7
VERTICAL CHEMICAL GRADIENTS SHORTER LIVED SPECIES
420
400
380
360
The
ta (
K)
10080604020Ethyne (pmol/mol)
420
400
380
360
The
ta (
K)
600500400300200100Ethane (pmol/mol)
420
400
380
360
The
ta (
K)
987654Chloroform (pmol/mol)
420
400
380
360
The
ta (
K)
454035302520Methylene Chloride (pmol/mol)
27% 28%
74% 78%
Bins of 10K θ
8
420
400
380
360
The
ta (
K)
1.00.80.60.40.20.0Bromoform (pmol/mol)
VERTICAL CHEMICAL GRADIENTS SHORTER LIVED SPECIES
420
400
380
360
The
ta (
K)
1816141210861,2 dichloroethane (pmol/mol)
420
400
380
360
The
ta (
K)
302520151050Methyl nitrate (pmol/mol)
420
400
380
360
The
ta (
K)
1.21.00.80.60.40.20.0C2Cl4 (pmol/mol)
75% 80%
36%69%
Bins of 10K θ
9
420
400
380
360
The
ta (
K)
302520151050Methyl nitrate (pmol/mol)
(?) ARTIFACT19x10
3
18
17
16
15
14
AL
T (
m)
120x1031101009080
UTC (sec)
10
FRACTIONS AT 366 K
360 380 400 4200
0.4
0.8
1.2
Potential Temperature (K)
Frac
tion
of m
ixin
g ra
tio a
t 366
K
7%
71%
75%
11
GROUPS FOR ORGANIC BROMINE BUDGET
TOTAL HALONS: HALON 1211+ (2*HALON 2402)+ HALON 1301
CH3Br= CH3Br
TOTAL SHOTER LIVED SPECIES (SLS) = (3* CHBr3)+ (2* CH2Br2) + CHBrCl2+ (2*CHBr2CL)+ CH2BrCL
BROMINATED SPECIES
HalonsHalon 1211 Halon 2402Halon 1301ChlorofluorocarbonsCFC-11 50 ACFC-12 102 ACFC-113 85 AHydrochlorofluoroarbons/ HydrofluorocarbonsHCFC_141b 9.4 AHCFC-22 13 AHCFC_142b 19.5 A
Solvent Carbon Tetrachloride 40 AMethyl chloroform 4.8 A
OtherCarbonyl Sulfide (COS) 30 N/A/BMethyl Chloride 1.5 N/B
Methyl HalidesBromoform Methyl BromideMethylene Bromide Methyl Iodide CHxBryClz
Solvents Yrs SMethylene Chloride 0.3 AChloroform 0.4 A/NTetrachloroethylene 0.3 ATrichloroethylene 0.02 A
Organic nitratesMethyl nitrate 0.08 A/NEthyl nitrate 0.04 A/NPropyl nitrate 0.03 A/N
Non- Methane Halocarbons Ethane (C2H6) 0.2 AEthyne 0.06 A/BPropane 0.04 ABenzene 0.04 A/B
Others1,2 dichloro ethane 0.3 AChlorobenzene 0.05 A
Longer Lived Species Shorter Lived Species Shorter Lived Species
SourcesA= antropogenic/industrialN= natural/marineB=Biomass burning
CBrClF2C2Br2F4CBrF3
• CHBrCl2 Bromodichloromethane• CHBr2Cl Dibromochloromethane• CH2BrCl Bromochloromethane
0.1 N0.8 A/N/B 0.4 N0.01 N 0.1 N
Methyl Bromide CH3Br
Yrs S 20 A20 A
CHBr3
CH2Br2
12
15
10
5
0
To
tal
Org
an
ic B
r, T
ota
l H
alo
ca
rbo
ns
, T
ota
l S
LS
, C
H3
Br
(pm
ol
of
Br/
mo
l)
410400390380370360350Potential Temp (K)
TOTAL ORGANIC BROMINE BUDGET
TOTAL HALONS
CH3Br
TOTAL SLS
TOTAL ORGANIC Br
Bins of 10K θ
13
ORGANIC BROMINE TENDENCYATTREX 2013 CR-AVE 2006
Total Organic BromineTotal HalonsTotal SLSCH3Br
Total Organic BromineHalonsShort lived BrCH3Br
Bins of 10K θ Measurements
25
20
15
10
5
0
390385380375370365360Potential Temp (K)
pmol
Br/
mol
14
ORGANIC BROMINE CONTRIBUTIONSGROUP CONTRIBUTIONS
SHORTER LIVED SPECIES DISTRIBUTIONS
41%
24%
35% 43%
20%
37%Total HalonsTotal SLSCH3Br
350-370 K 375-395 K
5%
46%
2%
6%
41%
6%
54%
3%
6%
31%CH2BrClCH2Br2CHBrCl2CHBr2ClCHBr3
15
TTL ORGANIC BROMINE COMPARISON
ATTREX-2 TC4 CR-AVE Year 2013 2007 2006Potential Temp 350-370 K 375-395K ~ 380-400 K 360-390 K
ppt sd ppt sd ppt sd ppt sd
TOTAL ORGANIC Br 19.46 1.36 18.34 1.20 17.3 1.4 17.1 1.0
SLBr 4.76 0.73 3.70 0.64 0.9 - 1.71 0.92Methyl bromide 6.77 0.23 6.81 0.23 8.1 0.5 7.85 0.17Halons 7.93 0.36 7.83 0.86 7.6 - 7.58 0.27
Fraction SLBr 0.24 0.15 0.20 0.17 0.05 - 0.10 0.05Fraction CH3Br 0.35 0.03 0.37 0.03 0.47 - 0.46 0.02Fraction Halons 0.41 0.04 0.43 0.11 0.43 - 0.44 0.03
16
43%
20%
37%
ORGANIC BROMINE FROM CAMPAIGNS
CR-AVE 2006
47% CH3Br
24% H1211
17% H1301
5.2 % H24015.2 %
CH2Br22.3%
sls
45.8% CH3Br
10 % SLS
15.2
% H
1301
23.9% H1211 5.2 % H2401
41%
24%
35%
Total HalonsTotal SLSCH3Br
350-370 K 375-395 K
44%
46%
43%
TC4 20075%
ATTREX 2013
17
SHORTER LIVED SPECIES COMPARISONATTREX 2013
5%
46%
2%
6%
41%
6%
54%
3%
6%
31%
CR-AVE 2006
350-370 K 375-395 K
64.5%
6.7%
4.1% 3.3%
17.4%3.7%
CH2BrClCH2Br2CHBrCl2CHBr2ClCHBr3C2H4Br2HalothaneWHY THE DIFFERENCES?
18
ATTREX-2 O3 MIXING RATIOS
18x103
17
16
15
14
AL
T (
m)
20100-10LAT (deg)
400
400
390
390
390 380
380
380
370
370
370
360
360
19
O3 AND SLBr SPECIES COMPARISON
0
50
100
150
200
250
300
350
400
320 340 360 380 400 420 440
ATTREX2TC4CRAVE
Ozo
ne (
ppbv
)
THETA
0
50
100
150
200
250
300
350
400
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6
ATTREX2TC4CRAVE
O3
_ppb
v
BROMOFORM (pptv)
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
0 0.2 0.4 0.6 0.8 1 1.2 1.4
ATTREX2TC4CRAVE
BR
OM
OF
OR
M
CH2BR2
20
Chlorofluorocarbons Yrs SCFC-11 50 ACFC-12 102 ACFC-113 85 A
HalonsHalon 1211 20 AHalon 2402 20 A
Hydrochlorofluoroarbons/ HydrofluorocarbonsHCFC_141b 9.4 AHCFC-22 13 AHCFC_142b 19.5 A
Solvent Carbon Tetrachloride 40 AMethyl chloroform 4.8 A
OtherCarbonyl Sulfide (COS) 30 N/A/BMethyl Chloride 1.5 N/B
Solvents Yrs SMethylene Chloride 0.3 AChloroform 0.4 A/NTetrachloroethylene 0.3 ATrichloroethylene 0.02 A
Methyl HalidesBromoform 0.1 NMethyl Bromide 0.8 A/N/BMethylene Bromide 0.4 NMethyl Iodide 0.01 NCHxBryClz 0.1 N
Organic nitratesMethyl nitrate 0.08 A/NEthyl nitrate 0.04 A/NPropyl nitrate 0.03 A/N
Non- Methane Halocarbons Ethane (C2H6) 0.2 AEthyne 0.06 A/BPropane 0.04 ABenzene 0.04 A/B
Others1,2 dichloro ethane 0.3 AChlorobenzene 0.05 A
Longer Lived Species Shorter Lived Species Shorter Lived Species
SourcesA= anthropogenic/industrialN= natural/marineB=Biomass burning
NATURAL AND ANTHROPOGENIC SPECIES
21
18x103
17
16
15
AL
T (
m)
20100-10LAT (deg)
400
400
390
390
390 380
380
380
370 370
360
360
18x103
17
16
15
AL
T (
m)
20100-10LAT (deg)
400
400
390 390
390 380
380
380
370 370
360
360
LATITUDINAL DISTRIBUTIONETHANE
18x103
17
16
15
AL
T (
m)
20100-10LAT (deg)
400 390
380
370
360
TETRACHLOROETHYLENE
BROMOFORM METHYL NITRATE
18x103
17
16
15
AL
T (
m)
20100-10LAT (deg)
400
400 390 380 380
370
370
360 360
pptv pptv
pptvpptv
22
SUMMARYLONGER AND SHORTER LIVED SPECIES• Mixing ratios of longer lived species change by less than 10%, while the mixing ratios of shorter lived species change around 70 to 75 % in the TTL
ORGANIC BROMINE BUDGET• Total organic bromine for ATTREX 2013 range between 19.5± 1.4 and 18.3 ± 1.2 pmol of Br/mol for potential temperature ranges of 350-370 and 375-395 K respectively. This value is also in similar to that found in previous campaigns
• However, contributions of SLS to the total organic bromine budget are slightly higher during ATTREX 2013. Delivery of 4.8 ±0.7 pmol/mol of organic bromine to the base of the TTL is estimated. Further analysis is needed.
NATURAL AND ANTHROPOGENIC SPECIES• Overall distributions reflect emission sources and lifetimes. Origins of higher concentration features will be diagnosed with trajectory analysis and other tracer correlations.
23
EXTRA SLIDES
24
GLOBAL HAWK WHOLE AIR SAMPLER (GWAS)
90 sample canisters
(custom Entech Inst.)
High vacuum solenoid valves (Parker Series 99)
Dual air compressor (Metal Bellows)
Computer controller (Custom built)
Fig 1: GWAS inside of the Global Hawk (area 61)
25
GLOBAL HAWK WHOLE AIR SAMPLER (GWAS) Includes:
• High Performance Gas Chromatograph / Mass Selective Detector/ Flame ionization detector / electron capture detector
• Unity 2TM Thermal Desorber
• CIA Advantage
• Variety of compounds analyzed with this instrument ( hydrocarbons, halocarbons, organic nitrates, solvents)
• Mixing ratios are calculated based on previous standard measurements and calibrations
26
LONGITUDINAL DISTRIBUTION
18x103
17
16
15
14
Alti
tude
(m
)
-160 -140 -120 -100LONGITUD (deg)
410
405
400
400
395
395
395 390
390
390
385
385
385 380
380 375
375
375
375
370
370
370
365
365
36
5
360
360 360 355
355
0.50.1
Bromoform
18x103
17
16
15
14
Alti
tude
(m
)
-160 -140 -120 -100LONGITUDE (deg)
410
405
400
400
395
395
395 390
390
390
385
385
385 380
380 375
375
375
375
370
370
370
365
365 3
65
360
360 360 355
355
302010Methyl Nitrate
18x103
17
16
15
14
Alti
tude
(m
)
-160 -140 -120 -100LONGITUDE (deg)
410
405
400
400
395
395
395 390
390
390
385
385
385
380
380 375
375
375
375
370
370
370
365
365
365
360
360 360 355
355
1.20.80.4Tetrachloroethylene
18
17
16
15
x103
-160 -140 -120 -100
400
400
390 380
380
380
370
370
360 360
500100ETHANE
27
VERTICAL CHEMICAL GRADIENTS
420
400
380
360
Th
eta
(K
)
454035302520Methylene Chloride (pmol/mol)
440
420
400
380
360
Th
eta
(K
)
5.24.84.44.0Methyl Chloroform (pmol/mol)
440
420
400
380
360
Th
eta
(K
)
0.80.60.40.2Halon 2402 (pmol/mol)
440
420
400
380
360
Th
eta
(K
)
300280260240220200180160HCFC-22 (pmol/mol)
440
420
400
380
360
The
ta (
K)
3028262422201816HCFC 142b (pmol/mol)
440
420
400
380
360
Th
eta
(K
)
560520480440400OCS (pmol/mol)
28
VERTICAL CHEMICAL GRADIENTS
440
420
400
380
360
Th
eta
(K
)
8.07.06.05.0Methyl Bromide (pmol/mol)
440
420
400
380
360
CH
4 T
AC
O :
-)
18001750170016501600UTC (sec)
440
420
400
380
360
Th
eta
(K
)
8.07.06.05.0Methyl Bromide (pmol/mol)
440420400380360
O3
12008004000UTC
29
VERTICAL CHEMICAL GRADIENTS
440
420
400
380
360
Th
eta
(K
)
0.300.250.200.150.100.050.00CH2BrCl (pmol/mol)
440
420
400
380
360
Th
eta
(K
)
0.150.100.050.00-0.05-0.10CH3I (pmol/mol)
440
420
400
380
360
Th
eta
(K
)
0.200.150.100.05CHBrCl2 (pmol/mol)
440
420
400
380
360
Th
eta
(K
)
0.50.40.30.20.1Chlorobenzene (pmol/mol)
30
VERTICAL CHEMICAL GRADIENTS
440
420
400
380
360
Th
eta
(K
)
50403020100Propane (pmol/mol)
440
420
400
380
360
Th
eta
(K
)
4321Ehtyl nitrate (pmol/mol)
440
400
360Th
eta
(K
)
1.20.80.40.0Isopropyl nitrate (pmol/mol)
440
400
360Th
eta
(K
)
121086420Benzene (pmol/mol)
31
correlations
30
25
20
15
10
5
MeO
NO
2 (p
mol
/mol
)
120010008006004002000O3 (ppb)
4.0
3.8
3.6
3.4
Hal
on 1
211
(pm
ol/m
ol)
120010008006004002000O3 (ppb)
1.0
0.9
0.8
0.7
0.6
0.5
CH
2Br2
(pm
ol/m
ol)
120010008006004002000O3 (ppb)
30
25
20
15
10
5
MeO
NO
2 (p
mol
/mol
)
8765CHCl3 (pmol/mol)
32
8.58.07.57.06.5
390
380
370
360
350
400350300250200
390
380
370
360
350
340
N2O
SF6
33
0
50
100
150
200
250
300
350
400
0 0.5 1 1.5
ATTREX2TC4
O3
_ppb
v
BROMOFORM (pptv)
34
0
50
100
150
200
250
300
350
400
320 340 360 380 400 420 440
ATTREX2
TC4O
zone
(pp
bv)
THETA
35
0
0.5
1
1.5
2
0 0.2 0.4 0.6 0.8 1 1.2 1.4
ATTREX2TC4
BR
OM
OF
OR
M
CH2BR2