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* Institute of Environmental Physics, Heidelberg
Bromine explosion in smog chamber experiments
above a model salt pan
Joelle Buxmann, Robert Holla, Ulrich Platt, Karsten Kotte,
University of Heidelberg, Germany
Natalja Balzer, Sergej Bleicher,Cornelius Zetzsch
University of Bayreuth, Germany
Funding by the DFG (German ResearchFoundation) within Research Unit HaloProc
and by the EU within Research Infrastructure EUROCHAMP-2
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Sua Pan<2ppt
Lake El‘Ton<2ppt [R.Holla]
Sebkha N‘Dramcha<2ppt
Walfish Bay<2ppt
Sal
Great Salt Lake6ppt [Stutz, 2002]
Salar de Uyuni~20ppt [Hönninger, 2004]
Dead Sea ~200ppt[Tas, 2008]
[Williams, 2002]
BrO above salt lakes and salt pans
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[Simpson 2007]
Bromine chemistry on salt surfaces
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[Simpson 2007]
Bromine chemistry on salt surfaces
BrONO2
NO2
BrONO2
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Analytical instruments:
• Multireflection system for DOAS detection of Br
• O3 analyzer
• NOx analyzer
• GC-FID with preconcentrator fortoluene, n-butane, n-pentane, 2,2-dimethylbutane, 2,2,3,3-tetramethyl-butane, and n-perfluorohexane
indirect determination of OH and Cl
Experimental setup
zero air
Salt sample
T1I
T2
T3
TH
O3 analyzer
NOx analyzer
GC-FID
DOAS
Solar simulator
IR Filter UV Filter
1.3 m
2.5 m
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s:
Experimental preparation
• Preparation of salt sample:artificial salt samples NaCl/NaBr = 300/1(similar to sea water) internal mixture (dissolved in water, dried over night , milled)
• Flush chamber over night with zero air by distilled water to „adjust“ relative humidity
• T=20°C (temperature controlled)
• Add O3(O2+UV light) and hydrocarbons• Switch solar simulator on
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DOAS spectra
338 340 342 344 346 348 350 352 354 356-2-1012
-2-1012
diffe
rent
ial o
ptic
al d
ensi
ty [*
10-3
]lo
g (in
tens
ity)
measurement spectrum
O3
-4-202
HCHO
BrO
1.0
1.1
-2-1012
wavelength [nm]
residual
BrO: 498 ±70 ppt
O3: 585 ppb
HCHO: 52 ppb
RH = 37%
(below detection limit)
(below detection limit)
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[O3] (“simple model“) = 2 k [BrO][BrO]= 0.005ppb/s
[O3](measured)=0.005ppb/s
-d
dt
with: k=2.7 *10-12 cm³ molec-1 s-1 [Atkinson, 2007] and [BrO]=200 ppt
-ddt
Experimental conditions: RH=2%, NaCl/NaBr=300/1
BrO + BrO → Br + Br + O2(rate determining)
2 (Br + O3 → BrO + O2)___________________________________net: 2 O3 → 3 O2
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BrO + BrO → Br + Br + O2(rate determining)
2 (Br + O3 → BrO + O2)
net: 2 O3 → 3 O2
[O3] (“simple model“) = 2 k [BrO][BrO]= 0.005ppb/s
[O3](measured)=0.005ppb/s
-d
dt
with: k=2.7 *10-12 cm³ molec-1 s-1 [Atkinson, 2007] and [BrO]=200 ppt
-ddt
Experimental conditions: RH=2%, NaCl/NaBr=300/1
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BrO + BrO → Br + Br + O2(rate determining)
2 (Br + O3 → BrO + O2)
net: 2 O3 → 3 O2
[O3] (“simple model“) = 2 k [BrO][BrO]= 0.005ppb/s
[O3](measured)=0.005ppb/s
-d
dt
with: k=2.7 *10-12 cm³ molec-1 s-1 [Atkinson, 2007] and [BrO]=200 ppt
-ddt
Experimental conditions: RH=2%, NaCl/NaBr=300/1
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BrO + BrO → Br + Br + O2(rate determining)
2 (Br + O3 → BrO + O2)
net: 2 O3 → 3 O2
[O3] (“simple model“) = 2 k [BrO][BrO]= 0.04ppb/s
[O3](measured)=0.03ppb/s
-d
dt
with: k=2.7 *10-12 cm³ molec-1 s-1 [Atkinson, 2007] and [BrO]=500 ppt
-ddt
Experimental conditions: RH=37%, NaCl/NaBr=300/1
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BrO + BrO → Br + Br + O2(rate determining)
2 (Br + O3 → BrO + O2)
net: 2 O3 → 3 O2
[O3] (“simple model“) = 2 k [BrO][BrO]= 0.04ppb/s
[O3](measured)=0.03ppb/s
-d
dt
with: k=2.7 *10-12 cm³ molec-1 s-1 [Atkinson, 2007] and [BrO]=500 ppt
-ddt
Experimental conditions: RH=37%, NaCl/NaBr=300/1
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BrO + BrO → Br + Br + O2(rate determining)
2 (Br + O3 → BrO + O2)
net: 2 O3 → 3 O2
[O3] (“simple model“) = 2 k [BrO][BrO]= 0.04ppb/s
[O3](measured)=0.03ppb/s
-d
dt
with: k=2.7 *10-12 cm³ molec-1 s-1 [Atkinson, 2007] and [BrO]=500 ppt
-ddt
Experimental conditions: RH=37%, NaCl/NaBr=300/1
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Very fast release of Br-sourced [BrO[ / dt = 40ppt/s
rate coefficient R= ¼ ·γ ·v ·A ,v~220m/s, A= effective surface~1m2/3,5m3
[Mochida et al., 1998],[Aguzzi and Rossi 1999]
Rate= 5 s-1
→ τ=200ms
Role of HO2 and NO2
RH=60%, NaCl/NaBr=300/1
BrOmax= 6420 ppt
Rate= 0.09 s-1
→ τ=11s
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OH
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OH and Cl
00:00 00:30 01:00 01:30 02:00 02:30 03:00-5.0x104
0.0
5.0x104
1.0x105
1.5x105
2.0x105
37% RH
Cl [
cm-3]
time [hh:mm]
0 2000 4000 6000 8000 10000
time [seconds]
at 37% RH:
[Cl]0 ≈ 3.5x104 cm-3
=> [ClO] ≈ 3.3x106cm-3
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Repeated exposure of salt pan at 60% RH: O3
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Repeated exposure of salt san at 60% RH: Br
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Repeated exposure of salt pan at 60% RH: BrO
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Three “bromine explosions”: Comparison
0 3600 7200 10800 14400
50
100
150
200
250
300
350
400
00:00 01:00 02:00 03:00 04:00
50
100
150
200
250
300
350
400
time [hh:mm]
O3
[ppb
]
rh 2% rh 30% rh 60%
00:00 01:00 02:00 03:00 04:000
1000
2000
3000
4000
5000
6000
7000 2% relative humidity 30% relative humidity 60% relative humidity
BrO
[ppt
]time [hh:mm]
2%2%
37%
37%
60% 60%
O3 BrO
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Discussion of humidity dependence: [BrO]max
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Discussion of humidity dependence: d[BrO]/dt
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Summary and Conclusions
First direct observation of “bromine
explosion” in laboratory
BrO up to 6000ppt
Strong dependence on relative
humidity
Controlled by thickness of quasi
liquid microlayer?
Fast Br-release for 60%rh is not
explained by reaction with HO2
alone.
NO2 might play a key role in
„bromine explosion“
00:00 01:00 02:00 03:00 04:00
1000
2000
3000
4000
5000
6000
7000
rh 2% rh 30% rh 60%
BrO
[ppt
]
time [hh:mm]
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Scattering by aerosol in the light path
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Thank you for your attention!