Trace gases measurements from the Global Hawk Whole

Trace gases measurements from the Global Hawk Whole

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 1 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 2 388 samples 45 vertical profiles GWAS on ATTREX-2 RF01 Altitude (m) RF03 RF04 RF01 RF03 RF04 RF05 RF06 RF05 RF06 UTC (sec) 3 ATTREX-2 TRACE GAS SPECIES FROM GWAS Longer Lived Species Chlorofluorocarbons CFC-11 CFC-12 CFC-113 Halons Halon 1211 Halon 2402 Shorter Lived Species Yrs 50 102 85 20 20

S A A A Solvents Yrs S Methylene Chloride 0.3 A Chloroform 0.4 A/N Tetrachloroethylene 0.3 A Trichloroethylene 0.02 A Hydrochlorofluoroarbons/ Hydrofluorocarbons HCFC_141b 9.4 HCFC-22 13 HCFC_142b 19.5 A Methyl Halides A Bromoform Methyl Bromide Methylene Bromide Methyl Iodide A CHxBryClz A A Solvent Carbon Tetrachloride Methyl chloroform A A 40 4.8 Other Carbonyl Sulfide (COS) 30 N/A/B Methyl Chloride 1.5 N/B 0.1 N 0.8 A/N/B 0.4 N 0.01 N 0.1 N Shorter Lived Species Organic nitrates Methyl nitrate Ethyl nitrate Propyl nitrate 0.08 A/N

0.04 A/N 0.03 A/N Non- Methane Halocarbons Ethane (C2H6) 0.2 A Ethyne 0.06 A/B Propane 0.04 A Benzene 0.04 A/B Others 1,2 dichloro ethane Chlorobenzene 0.3 0.05 A A Sources A= antropogenic/industrial N= natural/marine B=Biomass burning 4 AREA OF ANALYSIS ALT (Km) 18.3 27.0 LAT (deg) 5 VERTICAL CHEMICAL GRADIENTS LONGER LIVED SPECIES 4% 400 380 360 160 180 200 220 240 260 CFC-11 (pmol/mol) 400 280 300 2% 380 480 520

560 CFC-12 (pmol/mol) 400 600 7% 380 360 60 65 70 75 80 CFC-113 (pmol/mol) 85 90 4% 400 380 420 Theta (K) Theta (K) 380 420 360 420 2% 400 360 Theta (K) Theta (K) 420 Bins of 10K 420 Theta (K) Theta (K) 420 2.5 3.0 3.5

4.0 4.5 Halon 1211 (pmol/mol) 5.0 400 6% 380 360 360 16 18 20 22 24 26 28 HCFC 141b (pmol/mol) 30 60 70 80 90 CCl4 (pmol/mol) 100 110 6 VERTICAL CHEMICAL GRADIENTS SHORTER LIVED SPECIES 420 28% 27% 400 400 Theta (K) Theta (K) 420 380 380 360 360 20 25 30 35 40 Methylene Chloride (pmol/mol)

420 45 400 380 4 5 420 74% Theta (K) Theta (K) Bins of 10K 6 7 8 Chloroform (pmol/mol) 9 78% 400 380 360 360 100 200 300 400 500 Ethane (pmol/mol) 600 20 40 60 80 Ethyne (pmol/mol) 100 7 VERTICAL CHEMICAL GRADIENTS SHORTER LIVED SPECIES 400 75% 380 Theta (K) 420 Theta (K) Bins of 10K 420

400 80% 380 360 360 0.0 0.2 0.4 0.6 0.8 C2Cl4 (pmol/mol) 1.0 0 1.2 5 10 15 20 25 Methyl nitrate (pmol/mol) 420 420 69% Theta (K) Theta (K) 36% 400 380 360 30 400 380 360 6 8 10 12 14 16 1,2 dichloroethane (pmol/mol) 18 0.0 0.2 0.4

0.6 0.8 Bromoform (pmol/mol) 1.0 8 (?) ARTIFACT 3 ALT (m) 19x10 18 17 16 15 14 80 90 Theta (K) 420 100 110 UTC (sec) 3 120x10 400 380 360 0 5 10 15 20 25 Methyl nitrate (pmol/mol) 30 9 F r a c ti o n o f m ix in g r a ti o a t FRACTIONS AT 366 K 7% 1.2 71% 0.8 0.4 0 360 75% 380

400 420 Potential Temperature (K) 10 BROMINATED SPECIES Longer Lived Species Shorter Lived Species Shorter Lived Species Halons Yrs S Organic nitrates Methyl Halides Halon 1211 CBrClF2 20 A Methyl nitrate 0.08 A/N 0.1 N Bromoform CHBr3 Halon 2402 C2Br2F4 20 A 0.04 A/N 0.8CH3Br A/N/B Ethyl nitrate Bromide MethylMethyl Bromide Halon 1301 CBrF3 Propyl nitrate 0.03 A/N 0.4 N Methylene Bromide CH2Br2 Chlorofluorocarbons 0.01 N Methyl Iodide CFC-11 50 A CHxBryClz Non- Methane Halocarbons 0.1 N CFC-12 102 A Ethane (C2H6) 0.2 A CHBrCl2 Bromodichloromethane CFC-113 85 A Solvents Ethyne 0.06 A/B Yrs S CHBr2Cl Dibromochloromethane Hydrochlorofluoroarbons/ Propane 0.04 A Methylene Chloride 0.3 A CH2BrCl

Bromochloromethane Hydrofluorocarbons 0.04 A/B Chloroform 0.4 A/N Benzene HCFC_141b 9.4 A Tetrachloroethylene 0.3 A HCFC-22 GROUPS FOR 13 A ORGANIC BROMINE BUDGET Trichloroethylene 0.02 A Others HCFC_142b 19.5 A 1,2 dichloro ethane 0.3 A Chlorobenzene 0.05 A TOTAL HALONS: HALON 1211+ (2*HALON 2402)+ HALON 1301 Solvent Carbon Tetrachloride 40 A CH3Br= CH3Br Methyl chloroform 4.8 A Sources TOTAL SHOTER LIVED SPECIES (SLS) = (3* CHBr3)+ (2* CH2Br2) + CHBrCl2+ Other A= antropogenic/industrial Carbonyl Sulfide (COS) 30 CH2BrCL N/A/B (2*CHBr2CL)+ N= natural/marine Methyl Chloride 1.5 N/B B=Biomass burning 11 TOTAL ORGANIC BROMINE BUDGET Total Organic Br, Total Halocarbons, Total SLS, CH3Br (pmol of Br/mol) Bins of 10K TOTAL ORGANIC Br 15 10 TOTAL HALONS CH3Br 5 TOTAL SLS 0 350 360 370

380 390 Potential Temp (K) 400 410 12 ORGANIC BROMINE TENDENCY CR-AVE 2006 ATTREX 2013 25 pmol Br/mol 20 15 10 5 0 360 365 370 375 380 385 Potential Temp (K) Bins of 10K Total Organic Bromine Total Halons Total SLS CH3Br 390 Measurements Total Organic Bromine Halons Short lived Br CH3Br 13 ORGANIC BROMINE CONTRIBUTIONS GROUP CONTRIBUTIONS 375-395 K 350-370 K 35% 41% 24% 37% Total Halons Total SLS CH3Br 43% 20% SHORTER LIVED SPECIES DISTRIBUTIONS

5% 41% 46% 6% 2% CH2BrCl CH2Br2 CHBrCl2 CHBr2Cl CHBr3 6% 31% 6% 54% 3% 14 TTL ORGANIC BROMINE COMPARISON ATTREX-2 TC4 CR-AVE 2013 2007 2006 ~ 380-400 K 360-390 K Year Potential Temp 350-370 K 375-395K 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 0.92 Methyl bromide 6.77 0.23 6.81 0.23 8.1 0.5 7.85 0.17 Halons 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 0.05 Fraction CH3Br 0.35 0.03 0.37 0.03 0.47 - 0.46 0.02 Fraction Halons 0.41 0.04 0.43 0.11 0.43 - 0.44 0.03 15 ORGANIC BROMINE FROM CAMPAIGNS ATTREX 2013 375-395 K 350-370 K 35% 37% 41% 24%

TC4 2007 43% 20% Total Halons Total SLS CH3Br 5% CR-AVE 2006 44% 43% 17% H1301 47% CH3Br 45.8% CH3Br 24% H1211 23.9% H1211 46% 16 SHORTER LIVED SPECIES COMPARISON ATTREX 2013 350-370 K 375-395 K 5% 6% 41% 31% 46% 6% 6% 2% CR-AVE 2006 3% 4.1% 3.3% 6.7% 17.4% 64.5% WHY THE DIFFERENCES? 54% 3.7% CH2BrCl CH2Br2 CHBrCl2 CHBr2Cl CHBr3

C2H4Br2 Halothane 17 ATTREX-2 O3 MIXING RATIOS 3 18x10 390 380 370 17 400 380 390 390 370 16 380 15 370 ALT (m) 400 360 360 14 -10 0 10 LAT (deg) 20 18 O3 AND SLBr SPECIES COMPARISON 400 350 ATTREX2 TC4 CRAVE 300 O3_ppbv 250 200 150 250

200 150 100 100 50 50 0 320 ATTREX2 TC4 CRAVE 350 0 340 360 380 400 420 THETA 1.6 440 1.4 0 0.2 1 1.2 0.4 0.6 0.8 1 1.2 BROMOFORM (pptv) 1.4 1.6 ATTREX2 TC4 CRAVE 1.2 BROMOFORM Ozone (ppbv) 300 400 1 0.8

0.6 0.4 0.2 0 0 0.2 0.4 0.6 0.8 CH2BR2 1.4 19 NATURAL AND ANTHROPOGENIC SPECIES Longer Lived Species Chlorofluorocarbons CFC-11 CFC-12 CFC-113 Halons Halon 1211 Halon 2402 Shorter Lived Species Yrs 50 102 85 20 20 S A A A Solvents Yrs S Methylene Chloride 0.3 A Chloroform 0.4 A/N Tetrachloroethylene 0.3 A Trichloroethylene 0.02 A Hydrochlorofluoroarbons/ Hydrofluorocarbons HCFC_141b 9.4 HCFC-22 13 HCFC_142b 19.5 A Methyl Halides A Bromoform Methyl Bromide Methylene Bromide

Methyl Iodide A CHxBryClz A A Solvent Carbon Tetrachloride Methyl chloroform A A 40 4.8 Other Carbonyl Sulfide (COS) 30 N/A/B Methyl Chloride 1.5 N/B 0.1 N 0.8 A/N/B 0.4 N 0.01 N 0.1 N Shorter Lived Species Organic nitrates Methyl nitrate Ethyl nitrate Propyl nitrate 0.08 A/N 0.04 A/N 0.03 A/N Non- Methane Halocarbons Ethane (C2H6) 0.2 A Ethyne 0.06 A/B Propane 0.04 A Benzene 0.04 A/B Others 1,2 dichloro ethane Chlorobenzene 0.3 0.05 A A Sources A= anthropogenic/industrial N= natural/marine B=Biomass burning 20 LATITUDINAL DISTRIBUTION

ETHANE 3 3 18x10 400 390 380 17 16 360 -10 380 17 370 16 15 370 370 15 360 360 0 10 LAT (deg) -10 20 0 10 LAT (deg) 20 pptv pptv BROMOFORM 18x10 390 400 380 17

18x10 400 380 390 370 380 15 390 400 380 17 390 370 370 16 380 15 360 400 380 390 390 370 16 METHYL NITRATE 3 ALT (m) 3 ALT (m) 400 390 0 40 380 ALT (m)

ALT (m) 18x10 TETRACHLOROETHYLENE 360 360 360 -10 pptv 0 10 LAT (deg) 20 -10 0 10 LAT (deg) 20 21 pptv SUMMARY LONGER 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. 22 EXTRA SLIDES 23 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) 24 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 25 370 355 360 -160 -140 -120 LONGITUD (deg) -100 39 5 385 400 400 405 385 370 390 370 365 36 5 355 385 375 375 37

5 Altitude (m) 395 380 355 14 0.5 Bromoform 385 365 390 360 16 375 15 365 360 17 380 370 385 395 39 5 37 5 370 36 5 355 385 375 375 365 370 400 405 -100 0

39 400 380 395 -140 -120 LONGITUDE (deg) 410 395 390 18x10 0 385 15 0.1 -160 3 375 360 360 390 0.4 0.8 1.2 Tetrachloroethylene 39 Altitude (m) -100 41 0 16 360 355 14 -120 3 18x10 17 365

380 -140 370 370 -160 355 360 360 100 500 ETHANE 39 5 15 380 375 375 395 15 16 400 380 405 370 370 380 390 385 37 5 16 400 36 5 3 390 375

370 380 Altitude (m) 380 x10 17 400 395 0 39 17 410 3 18x10 400 365 18 385 390 LONGITUDINAL DISTRIBUTION 360 360 360 14 10 20 30 -160 Methyl Nitrate -140 -120 LONGITUDE (deg) -100 26 440 440 420 420 Theta (K) Theta (K)

VERTICAL CHEMICAL GRADIENTS 400 380 360 400 380 360 16 18 30 440 160 Theta (K) 28 420 400 380 420 180 200 220 240 260 HCFC-22 (pmol/mol) 280 300 400 380 360 360 0.2 440 0.4 0.6 Halon 2402 (pmol/mol) 420 0.8 400 380 4.0 4.4 4.8 5.2 Methyl Chloroform (pmol/mol) 420 Theta (K) Theta (K) Theta (K)

440 20 22 24 26 HCFC 142b (pmol/mol) 400 380 360 360 400 440 480 520 OCS (pmol/mol) 560 20 25 30 35 40 Methylene Chloride (pmol/mol) 2745 VERTICAL CHEMICAL GRADIENTS 440 420 Theta (K) Theta (K) 440 400 380 360 400 380 360 5.0 6.0 7.0 Methyl Bromide (pmol/mol) 8.0 440 420 400 380 360 5.0 6.0 7.0 Methyl Bromide (pmol/mol)

CH4 TACO :-) O3 420 0 400 800 UTC 1200 8.0 440 420 400 380 360 1600 1650 1700 1750 1800 28 UTC (sec) 440 440 420 Theta (K) 400 380 360 420 400 380 360 0.00 0.05 0.10 0.15 0.20 CH2BrCl (pmol/mol) 0.25 0.30 -0.10 440 440 420 420 Theta (K)

Theta (K) Theta (K) VERTICAL CHEMICAL GRADIENTS 400 380 360 -0.05 0.00 0.05 0.10 CH3I (pmol/mol) 0.15 400 380 360 0.1 0.2 0.3 0.4 Chlorobenzene (pmol/mol) 0.5 0.05 0.10 0.15 CHBrCl2 (pmol/mol) 0.20 29 VERTICAL CHEMICAL GRADIENTS 440 Theta (K) Theta (K) 440 420 400 380 400 360 360 4 0.0 1 2 3 Ehtyl nitrate (pmol/mol) 1.2 4 6 8 Benzene (pmol/mol)

12 440 440 420 Theta (K) Theta (K) 0.4 0.8 Isopropyl nitrate (pmol/mol) 400 380 400 360 360 0 10 20 30 40 Propane (pmol/mol) 50 0 2 10 30 correlations 1.0 25 0.9 CH2Br2 (pmol/mol) MeONO2 (pmol/mol) 30 20 15 10 0.8 0.7 0.6 5 0.5 0

200 400 600 800 O3 (ppb) 1000 0 200 400 600 800 O3 (ppb) 1000 1200 30 MeONO2 (pmol/mol) Halon 1211 (pmol/mol) 4.0 1200 3.8 3.6 3.4 25 20 15 10 5 0 200 400 600 800 O3 (ppb) 1000 1200 5 6 CHCl3 (pmol/mol) 7 8

31 SF6 390 380 370 360 350 6.5 7.0 7.5 8.0 8.5 N2O 390 380 370 360 350 340 200 250 300 350 400 32 400 350 ATTREX2 TC4 O3_ppbv 300 250 200 150 100 50 0 0 0.5 1 BROMOFORM (pptv) 1.5 33

400 350 ATTREX2 TC4 Ozone (ppbv) 300 250 200 150 100 50 0 320 340 360 380 400 THETA 420 440 34 2 ATTREX2 TC4 BROMOFORM 1.5 1 0.5 0 0 0.2 0.4 0.6 0.8 CH2BR2 1 1.2 1.4 35

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