1)Division of Marine and Atmospheric Chemistry, Rosenstiel School of Marine and Atmospheric Science,...
36
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 3) Atmospheric Chemistry and Climate Group, Institute of Physical Chemistry Rocasolano, CSIC, Madrid, Spain Geographical Distribution of Brominated Organic Trace Gases in the UT/LS region of the Pacific Maria Navarro 1 , E. Atlas 1 , A. Saiz-Lopez 3 , X. Rodriguez-Lloveras 3 , R. Lueb 1 , R. Hendershot 2 , S. Gabbard 2, D. Kinnison 2 , JF. Lamarque 2 , S.Tilmes 2 , C. Cuevas 3 , S. Schauffler 2 , V. Donets 1 , X. Zhu 1 , L. Pope 1 1
-
Upload
berenice-watts -
Category
Documents
-
view
213 -
download
0
Transcript of 1)Division of Marine and Atmospheric Chemistry, Rosenstiel School of Marine and Atmospheric Science,...
1
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, USA3) Atmospheric Chemistry and Climate Group, Institute of Physical Chemistry Rocasolano, CSIC, Madrid, Spain
Geographical Distribution of Brominated Organic Trace Gases in the UT/LS region
of the Pacific Maria Navarro1, E. Atlas1, A. Saiz-Lopez3, X. Rodriguez-Lloveras3, R. Lueb1, R. Hendershot2, S. Gabbard2, D. Kinnison2, JF. Lamarque2, S.Tilmes2, C. Cuevas3, S. Schauffler2, V. Donets1, X. Zhu1, L. Pope1
OBJECTIVESI- Characterize variability and distribution of organic bromine species in the UT/LS of the Eastern and Western Pacific.
II- Determine the amount of total very short lived brominated species (VSLBr =VSLorg + Bry) that enters the stratosphere.
• Examine the amount of inorganic bromine present at the Tropical Tropopause and the partitioning of these species from modeling results.
III- Examine the inter-hemispheric distribution of VSLorg.
3
MOTIVATION
• One of ATTREX questions: “What is the vertical distribution of BrO and short lived halogen compounds in the TTL and how does it vary seasonally and geographically?”
• Uncertainties on the amount of VSLBr reaching the stratosphere (2-8 ppt according to WMO-2014)
4
ATTREX locations and area of study
Longitude
Latit
ude
541 samples 68 vertical profiles
388 samples 45 vertical profiles
ATTREX-3 (2014) WESTERN PACIFIC ATTREX-2 (2013) EASTERN PACIFIC
165 187120 268
Global Hawk Whole Air Sampler (GWAS)
5
Trace Gas Species from GWAS
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 Halides Bromoform 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
SourcesA= antropogenic/industrialN= natural/marineB=Biomass burning
CBrClF2
C2Br2F4
CBrF3
0.1 N0.8 A/N/B 0.4 N0.01 N 0.1 N
Yrs S 20 A20 A
CHBr3
CH3BrCH2Br2
Yrs S
Shorter Lived Species
Minor VSLBr• Bromodichloromethane CHBrCl2
Dibromochloromethane CHBr2Cl Bromochloromethane CH2BrCl
6
CAM-Chem• Community Atmosphere Model (CAM V.5) (details in: Lamarque et
al., Geosci. Mod. Dev., 2012, Ordoñez et al., ACP, 2012 and Saiz-Lopez et al., ACP, 2012)
• Simulations with specific meteorological fields
• Vertical resolution: 56 levels (surface to ~ 993 hPa)
• Spatial resolution 1° x 1°
• Temporal resolution: 30 min
• Tropospheric Halogen Chemistry Chemical Processes• Halogen gas phase photochemistry (Cl, Br, and I)• Dry / wet deposition• Heterogeneous chemistry on sea-salt aerosols and ice particles• 9 additional VSL halocarbon species included.
Halogenated VSL sources from the ocean • Emissions following Chl-a over tropics (SeaWIFS)•Geographical and temporal distribution of VSL sources
7
Sampling Density of Organic Br Species
0
40
80
120
160
13 14 15 16 17 18 190
40
80
120
160
EASTERN
# Sa
mpl
es#
Sam
ples
Alt (Km)
WESTERNCH2BrCl
CH2Br2
CHBrCl2
CHBr2Cl
CHBr3
CH3Br
Halon 1211
Halon 2402
8
I- Variability and Distribution of GWAS Organic Bromine Species
18
17
16
15
14
x103
1.51.00.50
18
17
16
15
14
x103
1.51.00.50
Variability and Distribution of GWAS Organic Bromine SpeciesWESTERN PACIFIC EASTERN PACIFIC
Mixing ratios (pmol/mol)
Alt (
mts
)
Bin 1Km AltError =1sd
0.03% 1.3%
60% 49%
Halon 2402Halon 1211CH3Br
0.05% 1.96 % 1.3% 0.7 %
22% 17%
18
17
16
15
14
x103
8642
18
17
16
15
14
x10
3
8642
CHBr3
CH2Br2
Minor VSLBr
Minor VSL =CH2BrCl+CHBr2Cl +CHBrCl2
0 0.5 1 1.5
18
17
16
15
140 0.5 1 1.5
18
17
16
15
140 0.5 1 1.5
18
17
16
15
140 0.5 1 1.5
18
17
16
15
14
CAM-Chem: Variability and Distribution of Organic Bromine Species
WESTERN PACIFIC EASTERN PACIFIC
Halon 2402Halon 1211CH3Br
Minor VSLBrCHBr3
CH2Br2
0 0.5 1 1.5
18
17
16
15
140 0.5 1 1.5
18
17
16
15
140 0.5 1 1.5
18
17
16
15
140 0.5 1 1.5
18
17
16
15
14
0 1 2 3 4 5 6 7 8 9 10
18
17
16
15
14
0 1 2 3 4 5 6 7 8 9 10
18
17
16
15
14
0 1 2 3 4 5 6 7 8 9 10
18
17
16
15
14
0 1 2 3 4 5 6 7 8 9 10
18
17
16
15
14
0 1 2 3 4 5 6 7 8 9 10
18
17
16
15
140 1 2 3 4 5 6 7 8 9 10
18
17
16
15
140 1 2 3 4 5 6 7 8 9 10
18
17
16
15
140 1 2 3 4 5 6 7 8 9 10
18
17
16
15
14
Alt (
Km)
Mixing ratios (pmol/mol)Bin 1Km Alt Error model and measurements =1sd
11
18
17
16
15
14
18
17
16
15
0 1 2 3 4 5 6 7 8 9 10
18
17
16
15
140 1 2 3 4 5 6 7 8 9 10
18
17
16
15
140 1 2 3 4 5 6 7 8 9 10
Organic Bromine Species by Groups
WESTERN PACIFIC EASTERN PACIFIC
TOTAL HALONS = HALON 1211+ HALON 2402+ HALON 1301CH3Br = CH3BrVERY SHORT LIVED Br (VSLorg) = CHBr3+ CH2Br2 + CHBrCl2+ CHBr2Cl + CH2BrCl
pmol/mol
ALT
(km
)
VSlorg
CH3BrTotal Halons
18
17
16
15
14
18
17
16
15
0 1 2 3 4 5 6 7 8 9 10
Bin 1Km Alt Error model and measurements =1sd
12
II- VSLorg and Bry at the Tropical Tropopause
Organic Bromine Budget at the Tropopause (17Km)
TOTAL HALONS = HALON 1211+ (2*HALON 2402)+ HALON 1301
CH3Br = CH3Br
VERY SHORT LIVED Br (VSLorg) = (3* CHBr3)+ (2* CH2Br2) + CHBrCl2+ (2*CHBr2Cl)+ CH2BrClVERY SHORT LIVED Br (VSLorg) = (3* CHBr3)+ (2* CH2Br2) + Minor VSLBr
@ 17Km Western (pmol Br/mol) Eastern (pmol Br/mol)
Halons 7.59 ± 0.19 7.92 ± 0.11
CH3Br 7.16 ± 0.41 6.80 ± 0.23
VSLorg 3.27 ± 0.49 2.96 ± 0.42
Total Org Br Budget 18.02 ± 0.66 17.68 ± 0.49
ORGANIC BROMINE BUDGET
Br org budget =18.02± 0.66 pmol Br/mol Br org budget =17.68± 0.49 pmol Br/mol
40%
42%
18%
38%
45%
17%
WESTERN PACIFIC EASTERN PACIFIC
18% 17%
VSLorg
@ 17Km STRAT 1996(1) (%)
Halons 38
CH3Br 55
VSLorg 6.8
Total Org Br Budget (ppt) 17.4 ± 0.9
@ 17Km CRA-VE 2006 (%)
Halons 47
CH3Br 45
VSLorg 8
Total Org Br Budget (ppt) 17.5 ± 0.6
(1) Schauffier et al., GRL vol 25 # 3, 1998
VSlorg
CH3BrTotal Halons
Organic Bromine Budget at the Tropopause (17Km)
15
18
17
16
15
140 1 2 3 4 5 6 7 8 9 10
18
17
16
15
140 1 2 3 4 5 6 7 8 9 10
18
17
15
14
16
0 1 2 3 4 5 6 7 8 9 10
18
17
16
15
140 1 2 3 4 5 6 7 8 9 10
VSLOrg @ 17Km WESTERN PACIFIC EASTERN PACIFICGWAS measurements 3.27 ± 0.47 2.96 ± 0.42
WESTERN PACIFIC EASTERN PACIFIC
VSLOrg @ 17Km WESTERN PACIFIC EASTERN PACIFIC
GWAS measurements 3.27 ± 0.47 2.96 ± 0.42CAM-Chem 3.84 ± 0.64 3.18 ± 1.49
VSLorg in the Pacific Tropical Tropopause
Pmol Br/mol
Alt (
Km)
Minor VSLBrCHBr3
CH2Br2
VSLorg
16
18
17
16
15
140 1 2 3 4 5 6 7 8 9 10
18
17
16
15
140 1 2 3 4 5 6 7 8 9 100 1 2 3 4 5 6 7 8 9 10
18
17
16
15
14
18
17
16
15
140 1 2 3 4 5 6 7 8 9 10
WESTERN PACIFIC EASTERN PACIFIC
Bry @ 17Km WESTERN PACIFIC EASTERN PACIFIC
CAM-Chem 1.97 ± 0.21 3.02 ± 1.90
Inorganic Bromine in the Pacific Tropical Tropopause
Pmol Br/mol
Alt (
Km)
Minor VSLBrCHBr3
CH2Br2
VSLorg
Bry= Br+BrO+HOBr+BONO2+HBr+BrCl+2Br2+BrNO2+IBr
Bry
17
VSLorg @ 17Km WESTERN PACIFIC (ppt)
EASTERN PACIFIC (ppt)
GWAS measurements 3.27 ± 0.47 2.96 ± 0.42CAM-Chem 3.84 ± 0.64 3.18 ± 1.49
Bry @ 17Km WESTERN PACIFIC(ppt)
EASTERN PACIFIC(ppt)
CAM-Chem 1.97 ± 0.21 3.02 ± 1.90
VSLorg
𝐵𝑟 𝑦
VSLorg and Inorganic Bromine in the Tropopause
18
1.97±0.213.84±0.64
=𝟎 .𝟓𝟏±𝟎 .𝟎𝟒3.02±1.903.18 ±1.49
=𝟎 .𝟗𝟓±𝟎 .𝟑𝟐
WESTERN PACIFIC EASTERN PACIFIC
Bromine Fraction in the Pacific Tropical Tropopause
𝑩𝒓 𝒚
𝑽𝑺𝑳𝒐𝒓𝒈
Why do we have:
• Different Bry mixing ratios
• Similar VSLorg mixing ratios
• Abundance of Bry is ½ of the abundance of VSLorg in Western Pacific
• Abundance of Bry is similar to abundance of VSLorg in Eastern Pacific
• Since VSLorg mixing ratio is similar in both region, Bry mixing ratio in
the Eastern Pacific is twice than in the Western Pacific
19
VSLorg Emission fluxes
WESTERN PACIFIC EASTERN PACIFIC
Total VSLorg Emission WESTERN PACIFIC(10e+07 molecule/cm2/sec)
EASTERN PACIFIC(10e+07 molecule/cm2/sec)
CAM-Chem 3.7 5.5
In less convective area (LIKE THE EASTERN PACIFIC)• VSLorg have time to react more Bry production • Higher VSLorg emission compensate the loss due to rxn
0.24 0.42
3.00
0.36 0.61
4.50
CH2Br2
CH3BrMinor VSL
10e+07 molecule/cm2/sec
20
WESTERN PACIFIC EASTERN PACIFIC
VSLBr = VSLorg + Bry
(3.84 ±0.64)+(1.97±0.21) (3.18±1.49)+(3.02±1.90)
5.81 ± 0.67 ppt 6.20 ± 2.41 ppt
VSLBr (ppt) WESTERN EASTERNATTREX 5.81 (5.14-6.48) 6.20 (3.79-8.61)
Injection of Total VSL Brominated Species (VSLBr =VSLorg + Bry)
WMO (2014) ~ 5 (2-8)
ATTREX ESTIMATED ~ 6 (4-9) NARROW RANGE
21
• Inorganic Bromine Partitioning in the Pacific Tropical Tropopause
21
22
Sampling density and geographical distribution day and night
Western Pacific Eastern Pacific
day 146 81
night 28 210
No twilight samples (80 <TAS <100)
150°E 170°E 170°W 150°W 130°W 110°W
20°
S
0
°
2
0°N
4
0°N
Day twilight Night
20 40 60 80 100 120 140 160 180
60
50
40
30
20
10
0
Solar Zenith Angle
Num
ber o
f sam
ples
WesternEastern
23
0 2 4 6
18
17
16
15
140 2 4 6
18
17
16
15
140 2 4 6
18
17
16
15
140 2 4 6
18
17
16
15
140 2 4 6
18
17
16
15
140 2 4 6
18
17
16
15
14
Bry partitioning in the Pacific Tropical Tropopause
WESTERN PACIFIC EASTERN PACIFIC
DAY
NIGHT
Mixing ratio (ppt)
18
17
16
15
140 2 4 6
18
17
16
15
140 2 4 6
18
17
16
15
140 2 4 6
18
17
16
15
140 2 4 6
18
17
16
15
140 2 4 6
18
17
16
15
140 2 4 6
18
17
16
15
140 2 4 6
0 2 4 6
18
17
16
15
140 2 4 6
18
17
16
15
140 2 4 6
18
17
16
15
140 2 4 6
18
17
16
15
140 2 4 6
18
17
16
15
140 2 4 6
18
17
16
15
140 2 4 6
18
17
16
15
140 2 4 6
18
17
16
15
140 2 4 6
18
17
16
15
140 2 4 6
18
17
16
15
140 2 4 6
18
17
16
15
140 2 4 6
18
17
16
15
14
Br @ 17Km50.1 %
BrO @ 17Km47.8 %
BrONO2 @ 17Km50.1 %
BrCl @ 17Km57.7 %
Br BrNO2 +Br2HBrBrONO2HOBrBrOBrClIBr
Alt (
Km)
24
1 10 100 1000
18
17
16
15
14
1 10 100 1000
18
17
16
15
14
Modeled O3-NO2 and Cly mixing ratios
WESTERN PACIFIC EASTERN PACIFIC
Mixing ratios @ 17 km Western Pacific Eastern Pacific
O3 (ppb) 77.08 280.27
NO2 (ppt) 26.22 155.64
Cly (ppt) 8.26 117.06
Mixing ratio (ppb O3, ppt NO2 and Cly)
Alt (
km)
O3 (ppb) NO2 (ppt)Cly (ppt)
25
50 60 70 80 90 100 110 120
3
2
1
0
50 60 70 80 90 100 110 120 0.0
0.1
0.2
0.3
0.4
50 60 70 80 90 100 110 120 0
1
2
3
50 60 70 80 90 100 110 120 0.0
0.1
0.2
0.3
0.4
Bry partitioning in the tropical tropopause
O3 NO2 Cly
Solar Zenith Angle
Mix
ing
ratio
s N
O2(
ppb)
/Cl y (
ppb)
/O3(p
pm)
Mix
ing
ratio
s (p
pt)
Day twilight Night Day twilight Night
WESTERN PACIFIC EASTERN PACIFIC
Br= 50.1 %
BrO = 47.8 %
BrONO2=50.1% BrCl= 57.7 %
Br
HBrBrONO2
HOBr
BrOBrCl
Bry
26
III- Inter-hemispheric behavior of VSLBr
27
Inter-hemispheric sampling density
WESTERN PACIFIC EASTERN PACIFIC
13.0 14.0 15.0 16.0 17.0 18.00
20406080
100120140160180
13 14 15 16 17 180123456789
10
13 14 15 16 17 18 190
40
80
120
160
13 14 15 16 17 18 190123456789
10
# Sa
mpl
es#
Sam
ples
Alt (Km)
NORTH (0 to 36 °N)
SOUTH (0 to 11° S)
CH2BrCl CH2Br2 CHBrCl2 CHBr2Cl CHBr3 CH3Br Halon 1211 Halon 2402
280 2 4 6
18
17
16
15
14
18
17
16
15
14
0 2 4 6
0 2 4 6
18
17
16
15
140 2 4 6
18
17
16
15
14
Inter-hemisphericInter-hemispheric VSLBr distribution from GWAS and CAM-Chem
WESTERN PACIFIC EASTERN PACIFIC NORTH
SOUTH
Pmol Br/mol
Alt (
Km)
3.28 ± 0.49
3.16 ± 0.53
2.93 ± 0.42
3.30 ± 0.31
Minor VSLBrCHBr3
CH2Br2
VSLorg
29
Summary
• The Total Organic Bromine budget is approximately the same at 17 km (Θ ~ 370K) in the Eastern and Western Pacific ( ~ 18 ppt)
• In the less convective region (Eastern Pacific) VSLorg could have more time to react and produce ~1.5 times more Bry than in the most convective region (Western Pacific)
• Higher emissions of VSLorg in Eastern Pacific could compensate the losses due to reaction, and keep a similar amount of VSLorg in both regions of the Pacific (~ 3.8 ppt)
• The amount of VSLBr that reaches the stratosphere (17 Km) of the Eastern and Western Pacific is similar (~6 (4-9 ppt). The range observed in this study is significant narrow the one proposed by WMO 2014, particularly at the lower level.
• Partition of Bry species is different in the Eastern and Western Pacific. According to our model, during the day, Br is the dominant species the Western Pacific, while BrO dominates the Eastern Pacific. However, during the night, BrCl dominates in the West and BrONO2 dominates in the East.
• We don’t have enough samples from ATTREX to identify a significant interhemispheric difference in organic bromine.
Thank you and Questions
31
EXTRA SLIDES
32
33
Variability and Distribution of GWAS organic bromine speciesWESTERN PACIFIC EASTERN PACIFIC
Mixing ratios (pmol/mol)
ALT
(mts
)
18.0
17.0
16.0
15.0
14.0
x10
3
4.03.02.01.0
18.0
17.0
16.0
15.0
14.0
x10
3
9.08.07.06.0
18.0
17.0
16.0
15.0
14.0
x10
3
4.03.02.01.0
18.0
17.0
16.0
15.0
14.0
x10
3
9.08.07.06.0Bin 1Km AltError =1sd
Halon 1211Halon 2402
CH3Br
0.05%0.03%
1.96%
1.3%1.3%
0.7 %
34
Variability and Distribution of GWAS organic bromine speciesWESTERN PACIFIC EASTERN PACIFIC
Mixing ratios (pmol/mol)
ALT
(mts
)
18.0
17.0
16.0
15.0
14.0
x10
3
1.51.00.50.0
18.0
17.0
16.0
15.0
14.0
x10
3
1.51.00.50.0
CHBR3CH2Br2
CHBR2ClCH2BrClCHBrCl2
Bin 1Km AltError =1sd
60%22%
46%4 %16%
33 %7 %4 %
49%17%
35
Organic Bromine Budget in TTL (15-17Km)
WESTERN PACIFIC EASTERN PACIFIC
36%
19%
45%
Minor VSLBr ATTREX 2
21%
39%
40%
Minor VSLBr ATTREX 3
37%
44%
19%
Organic Br Budget ATTREX 2
39%
41%
20%
Org Br Budget ATTREX 3
CHBrCl2 46 CHBr2Cl 56
CH2BrCl 145
CH3Br
Total Halon
VSLorg
VERY SHORT LIVED Br (VSLorg) = (3* CHBr3)+ (2* CH2Br2) + Minor VSLBr
days
36
39%
41%
20%37%
44%
19%
Average Br org =18.48± x.xx pmol Br/mol Average Br org =18.19± x.xx pmol Br/mol
pmol Br/mol
Alt (
Km)
Bin 1Km AltError =1sd
36
CH3Br
Total Halons
VSLorg
CAM-ChemGWAS
Organic Bromine Budget in TTL (15-17Km)
Upper TTL
Lower TTL
![3 l] - Decapoda · 3 l] a U); Proceedings, Third International Coral Reef Symposium Rosenstiel School of Marine and Atmospheric Science University of Miami Miami, Florida 33149, U.S.A.](https://static.fdocuments.us/doc/165x107/5e58d8faf4aa9b5c21788d8b/3-l-decapoda-3-l-a-u-proceedings-third-international-coral-reef-symposium.jpg)
