Trace gases measurements from the Global Hawk Whole Air Sampler during the Airborne Tropical Tropopause Experiment 2013 (ATTREX-2) Maria Navarro 1, E. Atlas 1, R. Lueb 1, R. Hendershot 2, S. Gabbard 2, X. Zhu 1, L. Pope 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, 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

GWAS on ATTREX-2 RF01 RF03 RF04 RF05 RF06 Altitude (m) UTC (sec) 388 samples 45 vertical profiles 3

ATTREX-2 TRACE GAS SPECIES FROM GWAS Chlorofluorocarbons Yrs S CFC A CFC A CFC A Halons Halon A Halon A Hydrochlorofluoroarbons/ Hydrofluorocarbons HCFC_141b 9.4 A HCFC A HCFC_142b 19.5 A Solvent Carbon Tetrachloride 40 A Methyl chloroform 4.8 A Other Carbonyl Sulfide (COS) 30 N/A/B Methyl Chloride 1.5 N/B Solvents Yrs S Methylene Chloride 0.3 A Chloroform 0.4 A/N Tetrachloroethylene 0.3 A Trichloroethylene 0.02 A Methyl Halides Bromoform 0.1 N Methyl Bromide 0.8 A/N/B Methylene Bromide 0.4 N Methyl Iodide 0.01 N CHxBryClz 0.1 N Organic nitrates Methyl nitrate 0.08 A/N Ethyl nitrate 0.04 A/N Propyl nitrate 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 0.3 A Chlorobenzene 0.05 A Longer Lived Species Shorter Lived Species Sources A= antropogenic/industrial N= natural/marine B=Biomass burning 4

AREA OF ANALYSIS LAT (deg) ALT (Km) 5

VERTICAL CHEMICAL GRADIENTS LONGER LIVED SPECIES Bins of 10K θ 4%2% 7% 4% 6% 6

VERTICAL CHEMICAL GRADIENTS SHORTER LIVED SPECIES 27% 28% 74% 78% Bins of 10K θ 7

VERTICAL CHEMICAL GRADIENTS SHORTER LIVED SPECIES 75%80% 36% 69% Bins of 10K θ 8

(?) ARTIFACT 9

FRACTIONS AT 366 K 7% 71% 75% 10

GROUPS FOR ORGANIC BROMINE BUDGET TOTAL HALONS: HALON (2*HALON 2402)+ HALON 1301 CH3Br= CH3Br TOTAL SHOTER LIVED SPECIES (SLS) = (3* CHBr3)+ (2* CH2Br2) + CHBrCl2+ (2*CHBr2CL)+ CH2BrCL BROMINATED SPECIES Halons Halon 1211 Halon 2402 Halon 1301 Chlorofluorocarbons CFC A CFC A CFC A Hydrochlorofluoroarbons/ Hydrofluorocarbons HCFC_141b 9.4 A HCFC A HCFC_142b 19.5 A Solvent Carbon Tetrachloride 40 A Methyl chloroform 4.8 A Other Carbonyl Sulfide (COS) 30 N/A/B Methyl Chloride 1.5 N/B Methyl Halides Bromoform Methyl Bromide Methylene Bromide Methyl Iodide CHxBryClz Solvents Yrs S Methylene Chloride 0.3 A Chloroform 0.4 A/N Tetrachloroethylene 0.3 A Trichloroethylene 0.02 A Organic nitrates Methyl nitrate 0.08 A/N Ethyl nitrate 0.04 A/N Propyl nitrate 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 0.3 A Chlorobenzene 0.05 A Longer Lived Species Shorter Lived Species Sources A= antropogenic/industrial N= natural/marine B=Biomass burning CBrClF2 C2Br2F4 CBrF3 CHBrCl2 Bromodichloromethane CHBr2Cl Dibromochloromethane CH2BrCl Bromochloromethane 0.1 N 0.8 A/N/B 0.4 N 0.01 N 0.1 N Methyl Bromide CH3Br Yrs S 20 A CHBr3 CH2Br2 11

TOTAL ORGANIC BROMINE BUDGET TOTAL HALONS CH3Br TOTAL SLS TOTAL ORGANIC Br Bins of 10K θ 12

ORGANIC BROMINE TENDENCY ATTREX 2013 CR-AVE 2006 Total Organic Bromine Total Halons Total SLS CH3Br Total Organic Bromine Halons Short lived Br CH3Br Bins of 10K θ Measurements pmol Br/mol 13

ORGANIC BROMINE CONTRIBUTIONS GROUP CONTRIBUTIONS SHORTER LIVED SPECIES DISTRIBUTIONS 41% 24% 35% 43% 20% 37% Total Halons Total SLS CH3Br K K 5% 46% 2% 6% 41% 6% 54% 3% 6% 31% CH2BrCl CH2Br2 CHBrCl2 CHBr2Cl CHBr3 14

TTL ORGANIC BROMINE COMPARISON ATTREX-2TC4CR-AVE Year Potential Temp K K~ K K pptsdpptsdpptsdpptsd TOTAL ORGANIC Br SLBr Methyl bromide Halons Fraction SLBr Fraction CH3Br Fraction Halons

43% 20% 37% ORGANIC BROMINE FROM CAMPAIGNS CR-AVE % CH3Br 24% H % H % H % CH2Br2 2.3% sls 45.8% CH3Br 10 % SLS 15.2% H % H % H % 24% 35% Total Halons Total SLS CH3Br K K 44% 46% 43% TC % ATTREX

SHORTER LIVED SPECIES COMPARISON ATTREX % 46% 2% 6% 41% 6% 54% 3% 6% 31% CR-AVE K K 64.5% 6.7% 4.1% 3.3% 17.4% 3.7% CH2BrCl CH2Br2 CHBrCl2 CHBr2Cl CHBr3 C2H4Br2 Halothane WHY THE DIFFERENCES? 17

ATTREX-2 O3 MIXING RATIOS 18

O3 AND SLBr SPECIES COMPARISON 19

Chlorofluorocarbons Yrs S CFC A CFC A CFC A Halons Halon A Halon A Hydrochlorofluoroarbons/ Hydrofluorocarbons HCFC_141b 9.4 A HCFC A HCFC_142b 19.5 A Solvent Carbon Tetrachloride 40 A Methyl chloroform 4.8 A Other Carbonyl Sulfide (COS) 30 N/A/B Methyl Chloride 1.5 N/B Solvents Yrs S Methylene Chloride 0.3 A Chloroform 0.4 A/N Tetrachloroethylene 0.3 A Trichloroethylene 0.02 A Methyl Halides Bromoform 0.1 N Methyl Bromide 0.8 A/N/B Methylene Bromide 0.4 N Methyl Iodide 0.01 N CHxBryClz 0.1 N Organic nitrates Methyl nitrate 0.08 A/N Ethyl nitrate 0.04 A/N Propyl nitrate 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 0.3 A Chlorobenzene 0.05 A Longer Lived Species Shorter Lived Species Sources A= anthropogenic/industrial N= natural/marine B=Biomass burning NATURAL AND ANTHROPOGENIC SPECIES 20

LATITUDINAL DISTRIBUTION ETHANETETRACHLOROETHYLENE BROMOFORM METHYL NITRATE pptv 21

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 and 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 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 2 TM 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

LONGITUDINAL DISTRIBUTION 26

VERTICAL CHEMICAL GRADIENTS 27

VERTICAL CHEMICAL GRADIENTS 28

VERTICAL CHEMICAL GRADIENTS 29

VERTICAL CHEMICAL GRADIENTS 30

correlations 31

N2O SF6 32

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