Airborne Measurements of Halogens and Ozone Depletion at University of Manchester
Explore simultaneous measurements of bromine compounds and ozone depletion in the tropics conducted at the University of Manchester. Discover the research setup, data coverage, and issues faced during the study. Chemical Ionisation Soft (CIMS) techniques were utilized to analyze inorganic halogens. Get insights into the study's methodology, results, and ongoing calibration efforts.
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The University of Manchester, established in 1824. Simultaneous Airborne Measurements of BrO, HOBr, BrCl and Br2 in the Tropics: Inorganic Halogens and Subsequent O3 Depletion Michael Le Breton, Jennifer Muller, Kimberley Leather, Thomas Bannan, Steve Andrews, Shallcross, Asan Bacak & Carl Percival
The University of Manchester, established in 1824. Outline Instrumental setup - CIMS Data coverage Data results Modelling vs measured SS O3 depletion
The University of Manchester, established in 1824. Data coverage Flight duration CIMS data QCL data SP-2 Notes B823 B824 B825 B826 03:05 03:17 02:42 03:37 03:05 03:17 02:42 04:37 03:05 03:17 02:42 03:37 03:05 03:17 02:42 03:37 Data still needs to be worked up QCL Calibration needs to be worked on B827 03:13 04:13 03:13 03:13 B828 B829 B830 B831 B832 B833 B834 B835 B836 03:05 03:20 04:23 04:10 03:45 04:00 04:00 02:00 03:55 00:00 04:20 05:23 05:10 04:45 04:00 04:00 02:00 03:55 03:05 03:20 04:23 04:10 03:45 04:00 04:00 02:00 03:55 03:05 03:20 04:23 04:10 03:45 04:00 04:00 02:00 03:55 Power failure pre flight so no CIMS QCL Calibration needs to be worked on QCL Calibration needs to be worked on B837 03:45 03:45 03:45 03:45 B838 B839 B840 B841 B842 B843 B844 B845 B846 02:20 03:49 04:00 03:42 03:46 03:40 03:35 03:45 04:00 00:00 00:00 04:00 03:42 03:46 03:40 03:35 03:45 04:00 02:20 03:49 04:00 03:42 03:46 03:40 03:35 03:45 04:00 02:20 03:49 04:00 03:42 03:46 03:40 03:35 03:45 04:00 Overheating has affected CIMS data - being worked on Overheating has affected CIMS data - being worked on QCL Calibration needs to be worked on TOTAL 84:15 73:02 83:00 84:15 10 minute segments of QCL flights lost where software crashed % 100% 87% 96% 100%
The University of Manchester, established in 1824. The University of Manchester, established in 1824. Chemical Ionisation Soft ionisation High sensitivity A- + B B- + A reagent ion Flexible ionization molecule to detect Detect both + and ions ppt, LODs I- + HCOOH [HCOOH].I-
The University of Manchester, established in 1824. Manchester CIMS 22 Torr 0.24Torr 10-3 Torr 10-4 Torr
The University of Manchester, established in 1824. CIMS measurements 6 -.H2O 10 I - I 5 10 4 10 Ion counts Hz -.HCOOH I - N2O5 - Br 3 -.HNO3 10 I -.HCl I BrCl- -.BrCl -.HOBr I I-.HOBr.H2O -.BrO I I 2 -.ClNO2 10 I -.Br2 (active bromine) I 1 10 0 50 100 150 x10 200 250 300 3 species seen as mass sensitivity (ion counts per ppt) LOD (ppt) Formic acid Nitric acid Hydrogen chloride Butanoic acid I.HCOOH I.HNO3 I.HCl I.C3H7COOH 173 190 162 215 35 25 1.8 15 25 36 4 25 Nitrogen pentoxide NO3 62 27 1.9 Nitryl chloride I.ClNO2 208 34 33 Hydrogen cyanide I.HCN 154 33 0.4 Bromine monoxide I.BrO 222/224 16 0.8 Hypobromous acid I.HOBr.H2O 241 50 0.1 Bromine monochloride BrCl 113 50 0.1 Bromine I.Br2 287 100 0.1
The University of Manchester, established in 1824. BrO calibration HOBr , BrCl and Br2 all calibrated on FT NO 1. BrCl Cl2 and Br2 gas mixture equilibrate 2. HOBr AgNO3 (liberates Br) Mix with CCl4 (Removes Br2) Quantify with H+ and Br- 3. Br2 gas mixture and perm tube
[BrCl] ppt 14:00 13/02/2014 14:30 15:00 15:30 16:00 16:30 The University of Manchester, established in 1824. Time series example BrO Br2 BrCl HOBr O3 Altitude 80 Altitude (metres) 6000 5000 4000 3000 2000 1000 [O3] ppb 60 40 20 1.0 2.4 0.9 2.2 [BrO] ppt [Br2] ppt 0.8 2.0 0.7 1.8 0.6 1.6 0.5 1.0 2.8 0.9 2.6 [BrCl] ppt 0.8 [HOBr] ppt 2.4 0.7 2.2 0.6 2.0 0.5 1.8 14:00 14:30 15:00 15:30 16:00 16:30
The University of Manchester, established in 1824. B823 transit 30 20 10 altitude [ClNO2] [BrO] [N2O5] [O3] 1.5 0 11 500 400 300 200 100 [BrO] ppt 1.0 0.5 0 10 1.5 1.0 0.5 0.0 0.0 size is alt lat 9 80 60 40 20 8 8000 6000 4000 2000 landed in Palau from KK 0 132 134 136 lon 138 140 142 05:00 06:00 07:00 08:00 [ozone] ppb 19/01/2014 0 10 20 30 dat local time in Kota Kinabalu/Palau 8000 6000 altitude (metres) 1.5 4000 1.0 [BrO] 2000 8000 0.5 6000 altitude size is time (bigger is further into flight) 4000 2000 20 40 60 80 0.5 1.0 1.5 [BrO] ppt [ClNO2]
The University of Manchester, established in 1824. BrO and O3 data 1.6 KKIA - Kota Kinabalu PGUM - Guam TKK- Chuuk PTRO - Palau KKIA - PGUM TKK-TKK PGUM-TKK 1.4 TKK-TKK PTRO-PTRO 1.2 PGUM-PTRO PTRO-PTRO PGUM-TKK 1.0 [BrO] ppt TKK-TKK PGUM-PGUM PGUM-PGUM PGUM-PTRO PGUM-PGUM TKK-PGUM PGUM-PGUM 0.8 PGUM-PTRO PGUM-PGUM PTRO-PGUM PTRO-PTRO 0.6 PTRO-PGUM 0.4 0.2 19 B846 0 1 2 3 4 5 6 7 8 9 10 B835 11 B836 12 B837 13 B840 14 B841 15 B842 16 B843 17 B844 18 B845 B823 B834 B826 B832 B824 B825 B829 B827 B831 B830 Flight number KKIA - Kota Kinabalu PGUM - Guam TKK- Chuuk PTRO - Palau 80 PGUM-PTRO PGUM-PGUM PGUM-PGUM PGUM-PGUM PGUM-PTRO PTRO-PGUM 60 [O3] ppb PTRO-PTRO PGUM-PGUM PTRO-PTRO 40 PGUM-PTRO KKIA - PGUM PTRO-PTRO PGUM-TKK TKK-PGUM PTRO-PGUM TKK-TKK TKK-TKK TKK-TKK PGUM-TKK 20 PGUM-PGUM 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 B842 16 17 B844 18 19 B835 B836 B846 B823 B826 B830 B831 B843 B845 B824 B825 B828 B829 B834 B837 B840 B841 B832
The University of Manchester, established in 1824. Altitude profiles
The University of Manchester, established in 1824. O3 loss reactions 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. Br + O3 BrO + O3 Br + DMS products 11. 12 13a 13b 13c 14 15a 15b O3 + HO2 OH + 2O2 O3 + h O(1D) + O2 O(1D) + N2 O(3P) + N2 O(1D) + O2 O(3P) + O2 O(1D) + H2O OH + OH BrO + CH3O2 HOBr + CH2OO CH2OO OH + HO2 CH2OO + H2O HCOOH + H2O BrO + HO2 HOBr BrO + DMS Br + DMSO HOBr + h OH + Br Br2 + h Br + Br BrCl + h Br + Cl HOBr (wet deposition) BrCl (wet deposition) Br2(wet deposition)
The University of Manchester, established in 1824. O3 loss reactions Consider the four loss reactions O3HO2+O3 = k11[HO2][O3] 11. O3 + HO2 OH + 2O2 16. O3+ OH HO2 + O2 12 O3 + h O(1D) + O2 13c O(1D) + H2O OH + OH O3OH+O3 = k16[OH][O3] O3O1D = F1*J12[O3] F1 =k13C[H2O] / k13a[N2] + k13b[O2] + k13C[H2O] 1. Br + O3 BrO + O3 O3Br+O3 = k1[Br][O3]
The University of Manchester, established in 1824. SS approx for HO2 [HOBr] = k3[BrO][HO2] / J5 + J8] SS1 We don t know the wet deposition rate [HO2] = J5[HOBr] / K3[BrO] SS2 underestimate of HO2 or lower limit. [HO2] = J5 [HOBr] / K3[BrO] SS3
The University of Manchester, established in 1824. BrO Altitude profiles
The University of Manchester, established in 1824. CIMS case studies O3 + OH O3 + HO2 6000 Altitude (metres) 4000 2000 O3 + Br 1D O3 + O 20 40 60 80 % loss of O3
The University of Manchester, established in 1824. Summary and further work A suite of inorganics simultaneously measured in tropics on aircraft Also have measurements of formic, butanoic, nitric, HCN, ClNO2 and N2O5 CIMS measurements indicate model underestimates BrO by a factor of 3/4 Other inorganic halogens underestimated by similar factor Free Br dominated by inorganic photolysis Inorganic halogen photolysis responsible for up to 20% O3 loss in TMBL
