Supplement of Atmos. Chem. Phys., 15, 10799–10809, 2015
http://www.atmos-chem-phys.net/15/10799/2015/
doi:10.5194/acp-15-10799-2015-supplement
© Author(s) 2015. CC Attribution 3.0 License.
Supplement of
The NOx dependence of bromine chemistry in the Arctic atmospheric
boundary layer
K. D. Custard et al.
Correspondence to: K. D. Custard ([email protected])
The copyright of individual parts of the supplement might differ from the CC-BY 3.0 licence.
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Table S1. Gas-phase chemical reactions used in the model. All rate constants are calculated for a
temperature of 248 K unless otherwise noted and are expressed in units of cm3 molecule-1 s-1.
(Note: C2H5CHO represents propanal and C3H7CHO represents n-butanal)
____________________________________________________________________________________________________________
Reaction
Rate Constant
Reference
____________________________________________________________________________________________________________
O(1D) + M  O(3P)
3.34 x 10-11
Ravishankara et al. [2002]
3
O( P) + O2  O3
2.12 x 10-14
Atkinson et al. [2004]
O(1D) + H2O  2OH
2.2 x 10-10
Atkinson et al. [2004]
OH + O3  HO2
3.84 x 10-14
Atkinson et al. [2004]
OH + HO2  H2O
1.34 x 10-10
Atkinson e t al. [2004]
OH + H2O2  HO2 + H2O
1.52 x 10-12
Atkinson et al. [2004]
3
OH + O( P)  O2
3.74 x 10-11
Atkinson et al. [2004]
OH + OH  H2O + O(3P)
1.74 x 10-12
Atkinson et al. [2004]
OH + OH  H2O2
1.86 x 10-11
Atkinson et al. [2004]
OH + NO3  HO2 + NO2
2.0 x 10-11
Atkinson et al. [2004]
HO2 + NO3  HNO3
4.0 x 10-12
Atkinson et al. [2004]
HO2 + O3  OH + 2O2
1.39 x 10-15
Atkinson et al. [2004]
HO2 + HO2  H2O2 + O2
2.58 x 10-12
Atkinson et al. [2004]
NO + OH  HONO
NO + HO2  NO2 + OH
NO + O3  NO2
NO + NO3  NO2 + NO2
NO2 + OH  HNO3
NO2 + HO2  HNO4
NO2 + O3  NO3
NO2 + NO3  N2O5
NO2 + CH3COOO  PAN
NO3 + NO3  NO2 + NO2
N2O5 + H2O  HNO3 + HNO3
HONO + OH  NO2 + H2O
HNO3 + OH  NO3 + H2O
HNO4 + OH  NO2 + H2O
3.49 x 10-11
9.59 x 10-12
7.09 x 10-15
2.98 x 10-11
1.2 x 10-10
f: 8.6 x 10-12 r: 1.32 x 10-4
6.15 x 10-18
f: 1.83 x 10-12 r: 3.76 x 10-5
f: 1.4 x 10-11 r: 3.1 x 10-8
4.36 x 10-17
2.6 x 10-22
3.74 x 10-12
1.5 x 10-13
6.2 x 10-12
CO + OH  HO2 + CO2
CH4 + OH  CH3OO + H2O
C2H2 + OH  C2H2OH
C2H6 + OH  C2H5OO
C2H4 + OH  C2H4OH
C3H8 + OH  nC3H7O2
C3H8 + OH  iC3H7O2
C3H6 + OH  C3H6OH
C2H5CHO + OH  Products
nC3H7O2 + NO  NO2 + C3H6O + HO2
iC3H7O2 + NO  NO2 + CH3COCH3 + HO2
nC4H10 + OH  nC4H9OO
iC4H10 + OH  CH3COCH3 + CH3OO
nC4H9OO + NO  n-Butanal + NO2 + HO2
nC4H9OO + CH3OO  n-Butanal + HCHO + HO2 + HO2
nC4H9OO + CH3OO  n-Butanal + CH3OH
nC4H9OO + CH3OO  nC4H9OH + HCHO
CH3OH + OH  CH3O
n-Butanal + OH  Products
CH3OO + HO2  CH3OOH
C2H5OO + HO2  C2H5OOH
CH3COOO + HO2  CH3COOOH
2.4 x 10-13
1.87 x 10-15
7.8 x 10-13
1.18 x 10-13
1.02 x 10-11
1.56 x 10-13
6.64 x 10-13
3.63 x 10-11
2.51 x 10-11
5.4 x 10-11
1.2 x 10-11
1.64 x 10-12
1.65 x 10-12
5.4 x 10-11
6.7 x 10-13
2.3 x 10-13
2.3 x 10-13
7.09 x 10-13
2.0 x 10-11
8.82 x 10-12
1.12 x 10-11
2.54 x 10-11
Atkinson et al. [2004]
Atkinson et al. [2004]
Sander et al. [2006]
Sander et al. [2006]
Atkinson et al. [2004]
Atkinson et al. [2004]
Sander et al. [2006]
Atkinson et al. [2004]
Atkinson et al. [2004]
Sander et al. [2006]
Atkinson et al. [2004]
Sander et al. [2006]
Atkinson et al. [2004]
Atkinson et al. [2004]
Atkinson et al. [2004]
Sander et al. [2006]
Atkinson et al. [2004]
Lurmann et al. [1986]
hahtin et al. [2003]
Harris and Kerr [1988]
Harris and Kerr [1988]
Atkinson et al. [2004]
Atkinson et al. [2004]
Eberhard et al. [1996]
Eberhard and Howard [1996]
Donahue et al. [1998]
Donahue et al. [1998]
Michalowski et al. [2000]
Michalowski et al. [2000]
Michalowski et al. [2000]
Michalowski et al. [2000]
Atkinson et al. [2004]
Michalowski et al. [2000]
Atkinson et al. [2004]
Atkinson et al. [2004]
DeMore et al. [1997]
58
59
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61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
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81
82
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85
86
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90
91
92
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98
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100
101
102
103
104
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110
111
112
113
114
C2H5OOH + OH  C2H5OO
CH3OO + CH3OO  HCHO + HO2
CH3OOH + OH  HCHO + H2O + OH
CH3OOH + OH  CH3OO + H2O
CH3OO + HO2  CH3OOH
CH3OO + NO  HCHO + HO2 + NO2
CH3OO + NO2  CH3OONO2
CH3OO + nC3H7O2  HCHO + C3H6O + HO2 + HO2
CH3OO + nC3H7O2  C3H6O + CH3OH
CH3OO + nC3H7O2  HCHO + nC3H7OH
CH3OO + iC3H7O2  HCHO + CH3COCH3 + HO2 + HO2
CH3OO + iC3H7O2  CH3COCH3 + CH3OH
CH3OO + iC3H7O2  HCHO + iC3H7OH
CH3OO + C2H5OO  CH3CHO + HCHO + HO2 + HO2
CH3OO + CH3COOO  HCHO + CH3OO + HO2
C2H5OO + NO  CH3CHO + HO2 + NO2
C2H5OO + NO2  C2H5OONO2
C2H5OO + HO2  C2H5OOH
C2H5OO + CH3COOO  CH3CHO + CH3COO + HO2
iC3H7O2 + HO2  iPerox
nC3H7O2 + HO2  nPerox
HCHO + OH  HO2 + CO
HCHO + HO2  HOCH2O2
HCHO + NO3  HNO3 + HO2 + CO
CH3CHO + OH  CH3COOO + H2O
CH3CHO + NO3  HNO3 + CH3COOO
CH3COCH3 + OH  H2O + CH3COCH2
HOCH2O2 + NO  HCOOH + HO2 + NO2
HOCH2O2 + HO2  HCOOH + H2O
HOCH2O2 + HOCH2O2  HCOOH + HCOOH + HO2 + HO2
HCOOH + OH  HO2 + H2O + CO2
CH3COOO + NO  CH3OO + NO2 + CO2
CH3COOO + HO2  CH3COOH + O3
CH3COOO + CH3COOO  CH3COO + CH3COO
C2H5OONO2  C2H5OO + NO2
CH3OONO2 CH3OO + NO2
6.0 x 10-12
3.64 x 10-13
2.54 x 10-12
6.01 x 10-12
1.01 x 10-11
8.76 x 10-12
9.63 x 10-12
6.70 x 10-13
2.3 x 10-13
2.3 x 10-13
1.2 x 10-14
4.1 x 10-15
4.1 x 10-15
2.0 x 10-13
1.58 x 10-11
8.68 x 10-12
8.8 x 10-12
9.23 x 10-12
4.0 x 10-12
9.23 x 10-12
9.23 x 10-12
9.3 x 10-12
7.53 x 10-14
5.8 x 10-16
1.98 x 10-11
1.4 x 10-15
1.37 x 10-13
8.68 x 10-12
2.0 x 10-12
1.0 x 10-13
4.0 x 10-13
2.4 x 10-11
1.87 x 10-11
2.5 x 10-11
3.2 x 10-3
3.4 x 10-3
Cl2 + OH  HOCl + Cl
Cl + O3  ClO
Cl + H2  HCl
Cl + HO2  HCl
Cl + HO2  ClO + OH
Cl + H2O2  HCl + HO2
Cl + NO3  ClO + NO2
Cl + CH4  HCl + CH3OO
Cl + C2H6  HCl + C2H5OO
Cl + C2H4  HCl + C2H5OO
Cl + MEK  HCl
Cl + C2H2  ClC2CHO
Cl + C3H6  HCl + C3H6Cl
Cl + C3H8  HCl + iC3H7O2
Cl + C3H8  HCl + nC3H7O2
Cl + C3H6O  HCl
Cl + iC4H10  HCl + C4H9
Cl + nC4H10  HCl + C4H9
Cl + n-Butanal  HCl + Products
Cl + HCHO  HCl + HO2 + CO
2.85 x 10-14
1.02 x 10-11
3.5 x 10-15
3.57 x 10-11
6.68 x 10-12
2.11 x 10-13
2.4 x 10-11
3.99 x 10-14
5.36 x 10-11
1.0 x 10-10
4.21 x 10-11
2.5 x 10-10
2.7 x 10-10
1.65 x 10-10
1.65 x 10-10
1.1 x 10-10
1.3 x 10-10
2.15 x 10-10
1.1 x 10-10
7.18 x 10-11
Atkinson et al. [2004]
Lurmann et al. [1986]
Sander and Crutzen [1996]
Sander and Crutzen [1996]
Atkinson et al. [2004]
Atkinson et al. [2004]
DeMore et al. [1997]
Lightfoot et al. [1992]
Lightfoot et al. [1992]
Lightfoot et al. [1992]
Lightfoot et al. [1992]
Lightfoot et al. [1992]
Lightfoot et al. [1992]
Kirchner and Stockwell [1996]
Kirchner and Stockwell [1996]
Lurmann et al. [1986]
Atkinson et al. [1997]
Atkinson et al. [2004]
Michalowski et al. [2000]
Michalowski et al. [2000]
Michalowski et al. [2000]
Atkinson et al. [2004]
Sander et al. [2006]
DeMore et al. [1997]
Atkinson et al. [2004]
DeMore et al. [1997]
Atkinson et al. [2004]
Lurmann et al. [1986]
Lurmann et al. [1986]
Lurmann et al. [1986]
DeMore et al. [1997]
Atkinson et al. [2004]
Kirchner and Stockwell [1996]
Kirchner and Stockwell [1996]
Atkinson et al. [1997]
Atkinson et al. [1997]
Atkinson et al. [2004]
Atkinson et al. [2004]
Atkinson et al. [2004]
Sander et al. [2006]
Sander et al. [2006]
Atkinson et al. [2004]
Atkinson et al. [2004]
Sander et al. [2006]
Sander et al. [2006]
Atkinson et al. [2004]
Atkinson et al. [2004]
Atkinson et al. [2004]
Keil and Shepson [2006]
DeMore et al. [1997]
DeMore et al. [1997]
Wallington et al. [1988]
Hooshiyar and Niki [1995]
Tyndall et al. [1997]
Michalowski et al. [2000]
Sander et al. [2006]
115
116
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118
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120
121
122
123
124
125
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127
128
129
130
131
132
133
134
135
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140
141
142
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149
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161
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170
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Cl + CH3CHO  HCl + CH3COOO
Cl + CH3COCH3  HCl + CH3COCH2
Cl + CH3OOH  CH3OO + HCl
Cl + CH3OOH  CH2OOH + HCl
Cl + CHBr3  HCl + Br + CBr2O
Cl + OClO  ClO + ClO
Cl + ClNO3  Cl2 + NO3
Cl + PAN  HCl + HCHO + NO3
Cl + HNO3  HCl + NO3
Cl + NO2  ClNO2
Cl + HBr  HCl + Br
ClO + O(3P)  Cl + O2
ClO + OH  Cl + HO2
ClO + OH  HCl
ClO + HO2  HOCl
ClO + CH3OO  Cl + HCHO + HO2
ClO + CH3COOO  Cl + CH3OO + CO2
ClO + NO  Cl + NO2
ClO + NO2  ClNO3
ClO + ClO  Cl2
ClO + ClO  Cl + Cl
ClO + ClO  Cl + OClO
OClO + OH  HOCl
OClO + NO  ClO + H2O
HOCl + OH  ClO + H2O
HCl + OH  Cl + H2O
ClNO3 + OH  HOCl + NO3
HOCl + O(3P)  ClO + OH
8.08 x 10-11
1.39 x 10-12
2.36 x 10-11
3.54 x 10-11
2.9 x 10-13 (at 298 K)
6.35 x 10-11
1.12 x 10-11
1.0 x 10-14
1.0 x 10-16
1.43 x 10-12 (at 298 K)
4.48 x 10-12
1.6 x 10-11
2.45 x 10-11
2.37 x 10-13
8.67 x 10-12
2.08 x 10-12
2.03 x 10-12
2.04 x 10-11
7.1 x 10-12
1.64 x 10-15
1.54 x 10-15
1.40 x 10-15
1.13 x 10-11
1.51 x 10-13
4.0 x 10-13
6.84 x 10-13
3.17 x 10-13
1.7 x 10-13
Br + O3  BrO
Br2 + OH  HOBr
Br + HO2  HBr
Br + C2H2  BrCH2CHO
Br + C2H4  HBr + C2H5OO
Br + C3H6  HBr + C3H5
Br + HCHO  HBr + CO + HO2
Br + CH3CHO  HBr + CH3COOO
Br + C2H5CHO  HBr
Br + nButanal  HBr
Br + CH3OOH  HBr + CH3OO
Br + NO2  BrNO2
Br + NO2 ↔ BrONO
6.75 x 10-13
5.0 x 10-11
1.25 x 10-12
3.7 x 10-14
1.3 x 10-13
1.60 x 10-12
6.75 x 10-13
2.8 x 10-12
9.7 x 10-12
9.7 x 10-12
4.03 x 10-15
6.3 x 10-12
f: 6.3 x 10-12 r: 0.02
Br + BrNO2  Br2 + NO2
Br + BrONO  Br2 + NO2
Br + BrNO3  Br2 + NO3
Br + OClO  BrO + ClO
BrO + O(3P)  Br
BrO + OH  Br + HO2
BrO + HO2  HOBr
BrO + CH3OO  HOBr + CH2OO
BrO + CH3OO  Br + HCHO + HO2
BrO + CH3COOO  Br + CH3COO
BrO + C3H6O  HOBr
BrO + NO  Br + NO2
BrO + NO2  BrNO3
BrO + BrO  Br + Br
5.0 x 10-11
1.0 x 10-12
4.9 x 10-11
1.43 x 10-13
4.8 x 10-11
4.93 x 10-11
3.38 x 10-11
4.1 x 10-12
1.6 x 10-12
1.7 x 10-12
1.5 x 10-14
2.48 x 10-11
1.53 x 10-11
2.82 x 10-12
Atkinson et al. [2004]
Atkinson et al. [2004]
Atkinson et al. [2004]
Atkinson et al. [2004]
Kamboures et al. [2002]
Atkinson et al. [2004]
Sander et al. [2006]
Tsalkani et al. [1988]
Wine et al. [1988]
Ravishankara et al. [1988]
Nicovich and Wine [1990]
Atkinson et al. [2004]
Atkinson et al. [2004]
Sander et al. [2006]
Atkinson et al. [2004]
Sander et al. [2006]
Michalowski et al. [2000]
Atkinson et al. [2004]
Atkinson et al. [2004]
Atkinson et al. [2004]
Atkinson et al. [2004]
Atkinson et al. [2004]
Atkinson et al. [2004]
Atkinson et al. [2004]
Sander et al. [2006]
Atkinson et al. [2004]
Atkinson et al. [2004]
Atkinson et al. [2004]
Atkinson et al. [2004]
Atkinson et al. [2004]
Atkinson et al. [2004]
Atkinson et al. [2004]
Atkinson et al. [2004]
Atkinson et al. [2004]
Sander et al. [2006]
Atkinson et al. [2004]
Wallington et al. [1989]
Michalowski et al. [2000]
Mallard et al. [1993]
Atkinson et al. [2006]
Atkinson et al. [2006]
Orlando and Burkholder [2000]
Orlando and Burkholder [2000]
Orlando and Burkholder [2000]
Orlando and Tyndall [1997]
Atkinson et al. [2004]
Atkinson et al. [2004]
Atkinson et al. [2004]
Atkinson et al. [2004]
Aranda et al. [1997]
Aranda et al. [1997]
Michalowski et al. [2000]
Michalowski et al. [2000]
Atkinson et al. [2004]
Atkinson et al. [2004]
Sander et al. [2006]
172
173
174
175
176
177
178
179
180
181
182
183
184
185
186
187
188
BrO + BrO  Br2
BrO + HBr  HOBr + Br
HBr + OH  Br + H2O
CH3Br + OH  H2O + Br
CHBr3 + OH  H2O + Br
9.3 x 10-13
2.1 x 10-14
1.26 x 10-11
1.27 x 10-14
1.2 x 10-13
Sander et al. [2006]
Hansen et al. [1999]
Sander et al. [2006]
Atkinson et al. [2004]
Atkinson et al. [2004]
Cl + BrCl  Br + Cl2
f: 1.5 x 10-11 r: 1.1 x 10-15
Clyne and Cruse [1972]
Cl + Br2  BrCl + Br
f: 1.2 x 10-10 r: 3.3 x 10-1
Clyne and Cruse [1972]
BrO + ClO  Br + Cl
7.04 x 10-12
Atkinson et al. [2004]
BrO + ClO  BrCl
1.15 x 10-12
Atkinson et al. [2004]
BrO + ClO  Br + OClO
9.06 x 10-12
Atkinson et al. [2004]
HOBr + OH  BrO + H2O
5.0 x 10-13
Kukui et al. [1996]
HOBr + Cl  BrCl + OH
8.0 x 10-11
Kukui et al. [1996]
HOBr + O(3P)  BrO + OH
2.12 x 10-11
Atkinson et al. [2004]
____________________________________________________________________________________________________________
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190
191
192
193
194
195
196
197
198
199
200
201
202
203
204
205
206
207
208
209
210
211
212
213
214
215
216
217
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221
222
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228
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234
235
236
237
238
Table S2. Photochemical reactions. Jmax values for 25 March are shown as an example. J coefficients
are expressed in units of s-1.
____________________________________________________________________________________________________________
Reaction
Jmax 25 March
Lifetime
Source
____________________________________________________________________________________________________________
O3 + hv O2 + O(1D)
3.9 x 10-6
3.0 days
calculated from OASIS data
3
NO2 + hv NO + O( P)
8.6 x 10-3
1.9 min
calculated from OASIS data
H2O2 +hv OH + OH
3.4 x 10-6
3.4 days
calculated from OASIS data
NO3 +hv NO + O2
4.5 x 10-2
22 s
Michalowski et al. [2000]
N2O5 +hv NO2 + NO3
1.5 x 10-5
18 h
calculated from OASIS data
HONO +hv OH + NO
1.8 x 10-3
9.2 min
calculated from OASIS data
HNO3 +hv NO2 + OH
1.5 x 10-7
79 days
calculated from OASIS data
HNO4 +hv NO2 + HO2
7.3 x 10-7
16 days
calculated from OASIS data
HCHO +hv HO2 + HO2 + CO
1.5 x 10-5
19 h
calculated from OASIS data
HCHO +hv CO + H2
3.1 x 10-5
8.8 h
calculated from OASIS data
CH3CHO +hv CH3OO + HO2 + CO
1.1 x 10-6
11 days
calculated from OASIS data
CH3OOH +hv HCHO + HO2 + OH
3.2 x 10-6
3.7 days
calculated from OASIS data
C2H5CHO +hv HO2 + C2H OO + CO
1.4 x 10-6
8.3 days
calculated from OASIS data
PAN +hv CH3COOO + NO2
1.7 x 10-7
66 days
calculated from OASIS data
OClO +hv O(3P) + ClO
0.12
8.1 s
estimate from Pöhler et al. [2010]
Cl2 +hv Cl + Cl
2.1 x 10-3
8.1 min
calculated from OASIS data
ClO +hv  Cl + O(3P)
2.4 x 10-5
11 h
calculated from OASIS data
HOCl +hv  OH + Cl
1.4 x 10-4
2h
estimate from Lehrer et al. [2004]
ClNO3 +hv  Cl + NO3
2.9 x 10-5
9.5 h
calculated from OASIS data
ClNO3 +hv  ClO + NO2
3.4 x 10-6
3.4 days
calculated from OASIS data
BrNO3 +hv  Br + NO3
2.1 x 10-4
1.3 h
calculated from OASIS data
BrNO3 +hv  BrO + NO2
1.2 x 10-3
14.2 min
calculated from OASIS data
BrO +hv  Br + O(3P)
3.0 x 10-2
33 s
calculated from OASIS data
Br2 +hv  Br + Br
4.4 x 10-2
23 s
calculated from OASIS data
HOBr +hv  Br + OH
2.3 x 10-3
7.2 min
calculated from OASIS data
BrNO2 +hv  Br + NO2
5.7 x 10-3
2.9 min
estimate from Scheffler et al. [1997] &
Landgraf & Crutzen et al. [1998]
ClNO2 +hv  Cl + NO2
4.4 x 10-5
6.3 h
estimate from Ganske et al. [1992]
BrCl +hv  Br + Cl
1.26 x 10-2
1.3 min
calculated from OASIS data
____________________________________________________________________________________________________________
239
240
241
242
243
244
245
246
247
248
249
250
251
252
253
254
255
256
257
258
259
260
261
262
263
264
265
266
267
268
269
270
271
272
273
274
275
276
277
278
279
280
281
282
283
284
Table S3. Mass transfer reactions. All rate constants are expressed in units of s-1.
______________________________________________________________________________________
Reaction
k (forward)
k (reverse)
______________________________________________________________________________________
Particles
+
-3
HCl(g)  H (p) + Cl (p)
2.58 x 10
+
-3
HBr(g)  H (p) + Br (p)
1.80 x 10
-3
HOCl(g)  HOCl(p)
2.16 x 10
-3
HOBr(g)  HOBr(p)
1.26 x 10
-4
HOI(g)  HOI(p)
5.42 x 10
-5
OH(g)  OH(p)
3.26 x 10
-6
5
O3(g)  O3(p)
6.54 x 10
8.76 x 10
-5
7
Cl2(g)  Cl2(p)
2.69 x 10
2.96 x 10
-5
8
Br2(g)  Br2(p)
1.78 x 10
2.97 x 10
-4
10
BrCl(g)  BrCl(p)
6.60 x 10
1.91 x 10
-4
HNO3(g)  HNO3(p)
5.50 x 10
-4
N2O5(g)  N2O5(p)
1.08 x 10
-4
HONO(g)  HONO(p)
1.63 x 10
-5
PAN(g)  PAN(p)
2.05 x 10
-4
HNO4(g)  HNO4(p)
4.89 x 10
-3
ClNO2(g)  ClNO2(p)
1.26 x 10
-3
BrNO2(g)  BrNO2(p)
1.26 x 10
-3
ClNO3(g)  ClNO3(p)
1.26 x 10
-3
BrNO3(g)  BrNO3(p)
1.26 x 10
Snow
+
HBr(g)  H (s) + Br (s)
+
HCl(g)  H (s) + Cl (s)
HOBr(g)  HOBr(s)
HOCl(g)  HOCl(s)
OH(g)  OH(s)
O3(g)  O3(s)
Cl2(g)  Cl2(s)
Br2(g)  Br2(s)
BrCl(g)  BrCl(s)
HNO3(g)  HNO3(s)
N2O5(g)  N2O5(s)
HONO(g)  HONO(s)
PAN(g)  PAN(s)
HNO4(g)  HNO4(s)
ClNO2(g)  ClNO2(s)
BrNO2(g)  BrNO2(s)
ClNO3(g)  ClNO3(s)
BrNO3(g)  BrNO3(s)
-5
1.67 x 10
-5
1.67 x 10
-5
1.67 x 10
-5
1.67 x 10
-6
1.67 x 10
-6
1.67 x 10
-6
8.0 x 10
-5
1.0 x 10
-5
1.25 x 10
-5
1.67 x 10
-5
1.67 x 10
-5
1.67 x 10
-5
1.67 x 10
-5
1.67 x 10
-4
1.67 x 10
-4
1.67 x 10
-4
1.67 x 10
-4
1.67 x 10
-2
7.71 x 10
-2
7.71 x 10
-2
7.71 x 10
285
______________________________________________________________________
286
287
288
289
290
291
Table S4. Aqueous-phase reactions in the model. All aqueous reaction rate constants are converted to
units consistent to the gas-phase reactions to be read by the modeling program. For snow surface
reactions the measured aqueous phase reactions are divided by a conversion factor of 0.005 which
represents the liquid volume per snow surface cm2. For the particle reactions the measured aqueous
phase reactions are divided by 1.67x10-7 which represents the liquid volume conversion factor divided
by the height of the boundary layer, as in Michalowski et al. (2000)
292
293
294
* Third order rate constant, expressed in units of cm6·molecule-2·s-1
† second order rate constant, expressed in units of cm3·molecule-1·s-1
‡ first order rate constant, expressed in units of s-1
295
Reaction
Cl- + HOBr + H+ → BrCl *
Br- + HOCl + H+ → BrCl *
Br- + HOBr + H+ → Br2 *
Cl- + HOCl + H+ → Cl2 *
BrCl + Cl- → BrCl2- †
BrCl2- → BrCl + Cl- ‡
BrCl + Br- → Br2Cl- †
Br2Cl- →BrCl + Br- ‡
k (actual)
1.55 x 10-32
3.59 x 10-36
4.41 x 10 -32
6.07 x 10-38
1 x 10-11
1.58 x 109
1 x 10-11
3.34 x 105
k (particle)
5.17 x 10-21
1.2 x 10-24
1.47 x 10-20
2.02 x 10-26
3.3
1.58 x 109
3.3
3.34 x 105
k (snow)
9.30 x 10-26
2.15 x 10-29
2.64 x 10-25
3.63 x 10-31
5.99 x 10-5
1.58 x 109
5.99 x 10-5
3.34 x 105
Reference
(Wang et al., 1994)
(Sander et al., 1997)
(Beckwith et al., 1996)
(Wang and Margerum,
1994)
(Michalowski et al., 2000)
(Michalowski et al., 2000)
(Michalowski et al., 2000)
(Michalowski
et
al.,
2000;Wang et al., 1994)
296
297
298
299
300
301
302
303
304
305
306
Cl2 + Br- → BrCl2- †
1.28 x 10-11
4.27
7.66 x 10-5
BrCl2- → Cl2 + Br- ‡
6.94 x 102
6.94 x 102
6.94 x 102
O3 + Br- → HOBr †
OH + Cl- → HOCl †
N2O5 + Cl- → ClNO2 †
ClNO2 + H+ + Cl- → Cl2 †
1.35 x 10-20
1.35 x 10-20
1.66 x 10-12
1.66 x 10-14
4.5 x 10-9
4.5 x 10-9
5.5 x 10-1
5.5 x 10-3
8.08 x 10-14
8.08 x 10-14
9.94 x 10-5
9.94 x 10-8
N2O5 + Br- → BrNO2 †
BrNO2 + H+ + Br- → Br2 †
1.66 x 10-12
7.31 x 10-17
5.5 x 10-1
2.44 x 10-5
9.94 x 10-5
4.38 x 10-10
(Michalowski et al.,
2000;Beckwith et al.,
1996;Wang et al., 1994)
(Michalowski et al.,
2000;Wang et al., 1994)
(Michalowski et al., 2000)
assumed same as O3 + Brassume diffusion limited
estimated from (Roberts et
al., 2008)
assume diffusion limited
estimated from (Schweitzer
et al., 1998)
307
308
309
310
311
312
313
314
315
316
317
318
319
320
321
322
323
324
325
326
327
328
329
330
Table S5. Summary of the ambient measurements from OASIS that were used to constrain the model
and the instrumental method used. Constrained parameters were input into the model at 10 minute
intervals.
Measured Species
O3 and NOx
Method
Chemiluminescence
HONO
CO
Cl2 and Br2
HCHO
Long Path Absorption Photometer
CO Monitor
CIMS
Tunable Diode Laser Absorption
Spectroscopy
Online GC-MS
CH3CHO, CH3COCH3, MEK,
n-C4H10, i-C4H10, C2H5CHO
C2H2, C2H4, C2H6, C3H8,
n-C4H10, i-C4H10
Photolysis Frequencies
Method Reference
Ridley et al. [1992];
Ryerson et al. [2000];
Weinheimer et al., [1998]
Villena et al., [2011]
Liao et al. [2011, 2012]
Fried et al., [2003];
Lancaster et al. [2000]
Apel et al. [2010]
Canister samples, offline GC-MS
Russo et al. [2010]
Spectral Actinic Flux Density
Shetter and Muller et al. [1999]
331
332
333
Figure S1. 5 minute averages of observed concentrations of Br2 and NOx from OASIS 2009. It
should be noted that the Br2 axis has pptv units and the NOx axis has ppbv units.
334
335
(DeMore et al., 1997;Lightfoot et al., 1992;Ravishankara et al., 1988;Ravishankara et al., 2002;Sander et
al., 2006)
336
337
338
339
340
341
342
343
344
345
(Atkinson et al., 2004;Lehrer et al., 2004;Orlando and Tyndall, 1996;Lurmann et al., 1986;Vakhtin et al.,
2003;Harris and Kerr, 1988;Eberhard et al., 1996;Eberhard and Howard, 1996;Donahue et al.,
1998;Kirchner and Stockwell, 1996;Kukui et al., 1996;Keil and Shepson, 2006;Wallington et al.,
1988;Wallington et al., 1989;Apel et al., 2010;Tyndall et al., 1997;Kamboures et al., 2002;Tsalkani et al.,
1988;Nicovich and Wine, 1990;Wine et al., 1988;Lancaster et al., 2000;Russo et al., 2010;Shetter and
Muller, 1999;Mallard et al., 1993;Orlando and Burkholder, 2000;Aranda et al., 1997;Clyne and Cruse,
1972;Pohler et al., 2010;Ganske et al., 1992;Ridley et al., 1992;Weinheimer et al., 1998;Ryerson et al.,
2000;Villena et al., 2011;Liao et al., 2011;Liao et al., 2012;Fried et al., 2003)
346
347
348
349
(Sander and Crutzen, 1996;Hooshiyar and Niki, 1995)
350
351
352
353
Figure S2. Simulated BrONO2 mole ratio (low NOx & high NOx cases) plotted against the
production rate of BrONO2.
354
355
356
357
358
359
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361
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