Observation of large scale air pollution and its long-range transport transport using the European passenger aircraft system (CARIBIC) Carl A.M . Brenninkmeijer, CARIBIC coordinator, and Franz Slemr, MPI- Chemistry, Mainz Andreas Zahn and Herbert Fischer, IMK, Karlsruhe Markus Hermann and Jost Heintzenberg, IFT, Leipzig Hans Schlager and Helmut Ziereis, DLR, Oberpfaffenhofen David Oram and Stuart Penkett, UEA, Norwich Bengt Martinsson and Giorgos Papaspiropoulos, U. Lund Peter van Velthoven and Hans M. Cuypers, KNMI, de Bilt

Acknowledgements. LTU International Airways, , Ford Research, Ruhrgas, The European Ozone Research Coordinating Unit, The DGXII (FW4 - FW5 - FW6..

CARIBIC Aircraft

21 cm

CARIBIC Container CARIBIC: Currently Measured Species

A. In situ monitoring: O3 ,CO, H2O, NO, NOy, and aerosol concentration B. Aerosol samples (14): Aerosol elemental composition Si, S, K, Ca, Ti, Mn, Fe, Ni, Cu, Zn, ...

C. Air samples (12, extended to 30 samples, no isotopes) :

Greenhouse gases CO2, CH4, N2O, SF6 13 18 14 13 18 Stable isotopes and Carbon-14 CO: C, O, CO, CO2: C, O NMHCs: ethane, ethene, propane, propene, iso-butane, butane, acetylene, trans-2- butene, 1-butene, cis-2-butene, 2-methylbutane, pentane, propine, 1,3-butadiene, trans-2- pentene, cis-2-pentene, cyclohexane, 2-methylpentane, 3-methylpentane, hexane, isoprene Halogenated compounds: CFCs -11, -12, -13, -113, -114, -114a, -115, HCFCs -21, -22, -141b, -142b, -123, -124, HFCs -23, -134a, -143a, -152a, -125, Halons -1202, -1211, -1301, -2402,

CH3Br, CHBr3, CH2Br2, CH2BrCl, CHBrCl2, CHBr2Cl, COS C2H5Br, C2H4Br2, CH3Cl, CH2Cl2, CHCl3, C2Cl4, CH3CCl3, CF4, CCl4, C2F6, C3F8, c-C4F8, CH3I, C2H5I, CH2ClI, CH3CN, CH3ONO2, C2H5ONO2 CARIBIC flights LTU

Flight Routes

a. Maledives, Sri Lanka

b. South Africa, Namibia c. Cuba, Dominican Republic, Margerita

Air Masses

tropospheric air: ~83 %

stratospheric air: ~17 %

Longitude (oE) -20° 0° 20° 40° 60° 80°

50° 50°

Munich WAS-24-12 WAS-24-11 40° WAS-24-10 40° WAS-24-9

WAS-24-8 N)

o 30° 30° WAS-24-7 WAS-24-6

WAS-24-5 WAS-24-4 20° WAS-24-3 20°

Latitude ( Latitude WAS-24-2 10° WAS-24-1 10°

0° Male 0° CARIBIC Flight Male --> , 12 July 2000 20 50° 12 200 Temperature [°C]

10 Pressure [mbar] 0 40° 400 8 N) o 30° -20 6 600 20° 4 -40

Altitude [km] Altitude 800 Latitude ( Latitude 10° 2 Pot. Vorticity [PVU] Pot. Vorticity -60 0° 250 1000 100

200 400 80 nm 4 > Aerosols Aerosols >12nm WAS-24-1 WAS-24-2 WAS-24-3 WAS-24-4 WAS-24-5 WAS-24-6 WAS-24-7 WAS-24-8 WAS-24-9 WAS-24-10 WAS-24-11 WAS-24-12 [10 150 300 Ozone [ppb] 60 3 /cm 100 200 40 -3 ] CO [ppb] CO 50 100 20

0 0 -22 7 δ ] 80 14 18 oo CO (cm

-24 [°/ O(CO) 4 60 -26 1 -3

40 STP) C(CO) [°/ C(CO) oo 13

-28 ]

δ -2 20 -30 -5 1.90 376 325 5.0 320 4.8 1.85 372

315 N 4.6 SF 2 1.80 O [ppb]

310 6

368 [ppt] 4.4

[ppm] 305 [ppm] 4

1.75 2 364 4.2

CH 300 1.70 CO 295 4.0 360 1.65 290 3.8 Flight 24: Male - Munich, July 12, 2000

CO * 5 CH4-1300 Ethane Ethyne 700

600

500 ] tv

400 [pp ne y 300

200

100 , Eth an e , Eth ] bv 0 [pp 5 101520253035404550 Latitude [deg. N] CH4, CO CH4,

Longitude (o E) -20° 0° 20° 40° 60° 80°

50° 50° M unichWAS-25-12 40° WAS-25-11 40° WAS-25-10 30° WAS-25-9 30° 20° W AS-25-8 20° N)

o WAS-25-7

10° WAS-25-6 10° W AS-25-5 Colombo 0° W AS-25-4 0°

Latitude ( Latitude WAS-25-3 -10° WAS-25-2 -10° WAS-25-1 -20° -20° W indhoek -30° -30° CARIBIC Flight W indhoek --> M unich, 28 July 2000 20 50° 12 200

40° [°C] Temperature

10 Pressure [mbar] 0 30° 400 8 N) o 20° -2 0 600 10° 6 0° 4 -4 0

Altitude [km] Altitude 800 Latitude ( Latitude -10° 2 Pot. Vorticity [PVU] Vorticity Pot. -6 0 -20° 250 1000 100

200 400 80 nm 4 > Aerosols Aerosols >12nm WAS-25-1 WAS-25-2 WAS-25-3 WAS-25-4 WAS-25-5 WAS-25-6 WAS-25-7 WAS-25-8 WAS-25-9 [10 WAS-25-10 WAS-25-11 WAS-25-12 150 300 Ozone [ppb] 60 3 /cm

100 200 -3 40 ] CO [ppb] 50 100 20

0 0 -2 2 7 δ ] 80 14 18 oo CO (cm

-2 4 [°/ O(CO) 4 60 -2 6 1 -3

40 STP) C(CO) [°/ oo 13

-2 8 ]

δ -2 20 -3 0 -5 1.90 376 325 5.0 320 4.8 1.85 372

315 N 4.6 SF 2 1.80 O [ppb]

310 6

368 [ppt] 4.4 [ppm]

[ppm] 305 4

1.75 2 364 4.2

CH 300 1.70 CO 295 4.0 360 1.65 290 3.8 H alogenated Organic Trace G ases 4.5 60 Total 4.0 Total Organic 40 Organic Chlorine 3.5 Brom ine [p p b ] 20 [p p t] 3.0

2.5 0 06:00 08:00 10:00 12:00 14:00 16:00 Time (UTC )

Version 7-Sep-00; Zahn; WAS_25.OPJ Table 1: Comparison of CO enhancement ratios of samples 4 - 6 with previous results reported for fresh plumes of biomass burning.

Species Background a) ER (∆Χ/∆CO) b) SH NH Sample 4 Sample 5 Sample 6 Literature d) Literature e) f) g) (Samples 2, 3) (Samples 7,8,9) (SH) (SH) (NH) CO 75 ± 1 89 ± 5 c) c) d) e) f) CH4 1744.3 ± 0.1 − 0.159 ± 0.016 0.227 ± 0.035 - 0.16 - 0.37 0.08 - 0.12 d) e) f) C2H6 427 ± 14 465 ± 15 3.4 ± 0.2 5.1 ± 0.3 5.1 ± 1.3 4 - 9 4.5 - 8.9 d) e) f) C3H8 32 ± 3 52 ± 2 0.68 ± 0.05 1.58 ± 0.08 0.78 ± 0.20 0.9 – 2.4 0.9 - 1.7 d) e) f) C4H10 4.6 ± 1.4 7.9 ± 1.0 0.07 ± 0.03 0.43 ± 0.04 0.1 ± 0.1 0.1 – 0.4 0.15 - 0.23 - d) e) f) iC4H10 1.3 ± 0.7 2.9 ± 0.2 0.04 ± 0.01 0.24 ± 0.02 0.09 ± 0.03 0.04 - 0.07 e) d) f) C2H2 101 ± 5 113 ± 13 3.9 ± 0.2 3.6 ± 0.3 2.9 ± 0.9 1 – 10 2.0 - 4.8 d) e) f) C6H6 36 ± 3 45 ± 5 0.9 ± 0.1 1.0 ± 0.1 1.3 ± 0.4 0.8 – 1.5 1.3 - 1.7 -3 -3 -3 -3 d) e) f) CH3Br 10.3 ± 0.3 10.5 ± 0.2 (6 ± 5)·10 (10 ± 5)·10 (67 ± 19)·10 - (5.5 - 10.3)·10 d) e) f) CH3Cl 584 ± 13 594 ± 18 0.2 ± 0.2 0.3 ± 0.2 0.2 ± 0.8 0.7 – 1.1 0.12 – 0.57 -3 -3 -3 -3 d) e) f) CH3I 0.12 ± 0.02 0.12 ± 0.02 (6 ± 1)·10 (7 ± 1)·10 (11 ± 3)·10 - (1.2 - 14)·10

a) Units are ppbv for CO and CH4 and pptv for all other compounds b) Units are ppbv/ppbv for ∆CH4/∆CO and pptv/ppbv for all other ratios. c) No background value could be defined for CH4 in the NH. d) Mauzerall et al. [1998] and Andreae et al. [2001] and references therein] e) Blake et al. [1996b] f) Ferek et al. [1998] g) Blake et al. [1997] Longitude (o E) -80° -60° -40° -20° 0° 20°

Düsseldorf 50° W AS-33-12 50° W AS-33-11 W AS -33-10 W AS-33-9 40° W AS-33-8 40° W AS -33-7 W AS-33-6

N) W AS-33-5 o 30° WAS-33-4 30°

W AS -33-3 W A S-33-2 Holguin W AS-33-1 Latitude ( Latitude 20° 20°

10° 10°

CARIBIC Flight Holguin --> Düsseldorf, 14 M ay 2001 20 50° 12 200 Temperature [°C]

10 Pressure [mbar] 0 40° 400 8 N) o 30° -2 0 6 600 20° 4 -4 0

Altitude [km] Altitude 800 Latitude ( Latitude 10° 2 Pot. Vorticity [PVU] Vorticity Pot. -6 0 0° 250 1000 40

200 400 nm 4 > Aerosols Aerosols > 12nm 30 WAS-33-1 WAS-33-2 WAS-33-3 WAS-33-4 WAS-33-5 WAS-33-6 WAS-33-7 WAS-33-8 WAS-33-9 WAS-33-10 WAS-33-11 WAS-33-12 [10 150 300 Ozone [ppb] 3

/cm 20 100 200 -3 ] CO [ppb] CO 10 50 100

0 0 -2 2 16 δ ] 13 80 14

-2 4 18 oo CO (cm 10 [°/ O(CO) -2 6 7 60 -2 8 4 -3

40 STP) C(CO) [°/ oo

13 1 -3 0 ] δ -2 20 -3 2 -5 1.90 376-3 4 325 5.0 1.85 320 4.8 372 315 N

1.80 4.6 SF 2

310 O [ppb] 6

368 [ppt] 1.75 305 4.4 [ppm] [ppm] 4 1.70 2 364 300 4.2 CH CO 295 1.65 4.0 360 290 1.60 285 3.8 H alogenated O rganic Trace G ases 4.5 60 Total 4.0 Total Organic 40 O rganic Chlorine 3.5 Brom ine [ppb] 20 [ppt] 3.0

2.5 0 22:00 24:00 26:00 28:00 30:00 Time (UTC )

From : the new LUFTHANSA Airbus A340-600 Aircraft CARIBIC inlet system: Inlet side view

sampling lines

air flow outlet

camera

180 a: NOx, O3, MS, cloud sensor tube b: H2O, CO, CO2, WAS tube 13 shroud heated tip

diffuser 50

3 - 4 strut mountings c: aerosol tube

480 mm 3/7 CARIBIC partners

MPI-Chemistry: coordination, container operation, CO and H2O continuously, trace gas, isotope, and NMHC analysis of air samples

IMK, Karlsruhe: O3, selected organic compounds continuously by PTR- MS IFT, Leipzig: aerosols by 3 CNCs and optical particle counter DLR, Oberpfaffenhofen: NO and NOy continuously GKSS, Geesthacht: Hg semicontinuously

CEA/CNRS, Paris: CO2 continuously UEA, Norwich: halocarbon analysis of air samples U. Lund: analysis of aerosols for elements and organic compounds KNMI, de Bilt: meteorological analysis and trajectories