A A. Reactions and rates of the CBM-IV chemical mechanism
In this annex we describe the full CBM-IV chemical mechanism of LOTOS-EUROS
Table xx ??. The CBM-IV mechanism used in LOTOS-EUROS. Reaction rates (ppb-x min-1) are to be calculated as k= A*exp(-E/(RT)). Photolysis reactions are indicated with J. ch2o is the water concentration in ppm
|
Nr |
Reactie |
A |
-E/R |
Ref |
|
1J |
NO2 + hv à NO + O3 |
|
|
|
|
2 |
O3 + NO à NO2 |
2.952 |
-1450 |
|
|
3 |
O3 + NO2 à NO3 |
0.176 |
-2450 |
|
|
4J |
O3 + hv à a1*O3 + a2*OH |
|
|
|
|
5 |
O3 + OH à HO2 |
2.362 |
-940 |
|
|
6 |
O3 + HO2 à OH |
1.62e-2 |
-580 |
|
|
7 |
NO3 + NO à 2NO2 |
22.14 |
170 |
|
|
8 |
NO3 + NO2 à NO + NO2 |
3.66e-2 |
-1230 |
|
|
9 |
NO3 + NO2 à N2O5 |
|
|
|
|
10 |
N2O5 +h2o à 2 HNO3 |
1.92e-6*ch2o |
|
|
|
11 |
N2O5 à NO3 + NO2 |
2.11e16 |
-10897 |
|
|
12 |
NO + NO2 + H2O à 2HONO |
1.6e-14*ch2o |
|
|
|
13 |
HONO + HONO à NO + NO2 |
1.48e-8 |
|
|
|
14J |
HNO2 + hv à OH + NO |
|
|
|
|
15 |
NO2 + OH àHNO3 |
|
|
|
|
16 |
NO + OH à HONO |
|
|
|
|
17 |
HO2 + NO à OH + NO2 |
5.46 |
240 |
|
|
18 |
NO + NO à 2NO2 |
2.66e-8 |
530 |
|
|
19 |
OH + HONO à NO2 |
9.74 |
|
|
|
20J |
NO3 + hv à NO2 + O3 |
|
|
|
|
21J |
NO3 + hv à NO |
|
|
|
|
22 |
HO2 + HO2 à H2O2 |
0.339 |
600.0 |
|
|
23 |
HO2 + HO2 + H2Oà H2O2 |
6.9e-8*ch2o |
980 |
|
|
24 |
OH + CO à HO2 |
0.325 |
|
|
|
25 |
FORM + OH --> HO2 + CO |
14.76 |
|
|
|
26J |
FORM + hv à 2 HO2 +CO |
|
|
|
|
27J |
FORM + hv à CO |
|
|
|
|
28 |
FORM + NO3 à HNO3 +HO2 + CO |
9.3e-4 |
|
|
|
29 |
ALD + OH à C2O3 |
10.33 |
250 |
|
|
30 |
ALD + NO3 à C2O3 + HNO3 |
3.7e-3 |
|
|
|
31J |
ALD + hv à XO2 +2HO2 + CO +FORM |
|
|
|
|
32 |
C2O3 + NO à NO2 + XO2 + FORM + HO2 |
7.97 |
250 |
|
|
33 |
C2O3 + NO2 à PAN |
1.18e-7 |
5500 |
|
|
34 |
PAN à C2O3 + NO2 |
5.64e18 |
-14000 |
|
|
35 |
c2o3 +c2o3 à XO2 + 2 FORM + 2HO2 |
3.7 |
|
|
|
36 |
C2O3 + HO2 à 0.79*(FORM + HO2 + XO2 + OH) |
9.6 |
|
|
|
37J |
MGLY + hv à C2O3 + HO2 + CO |
|
|
|
|
38 |
MGLY + OH à XO2 + C2O3 |
25.1 |
|
|
|
39 |
CH4 + OH à XO2 + FORM + HO2 |
3.91 |
-1800 |
|
|
40 |
PAR + OH à 1.49 XO2 + 0.067XO2N + 0.93 HO2 + 0.45 ALD2 -0.75 PAR |
1.203 |
|
|
|
41 |
OH + OLE à FORM + ALD2 + XO2 + HO2 - PAR |
7.67 |
504 |
|
|
42 |
O3 + OLE à 0.5ALD2 + 0.74FORM + 0.33CO + 1.7HO2 + 0.1OH - PAR |
2.066e-2 |
-2105 |
|
|
43 |
NO3 + OLE à 0.91XO2 + 0.09 XO2N + FORM + ALD2 - PAR + NO2 |
1.137e-2 |
|
|
|
44 |
OH + ETH à XO2 + 1.56FORM + HO2 + 0.22ALD2 |
2.95 |
411 |
|
|
45 |
O3 + ETH à FORM + 0.42CO + 0.12HO2 |
1.92e-2 |
-2633 |
|
|
46 |
OH + TOL à 0.08XO2 + 0.36CRES + 0.44HO2 + 0.56TO2 |
3.106 |
322 |
|
|
47 |
PHEN (CRES) + NO3 à PHO (PHO) + HNO3 |
32.47 |
|
|
|
48 |
PHO + NO2 à |
20.0 |
|
|
|
49 |
XYL + OH à 0.7HO2 + 1.1PAR + 0.8MGLY + 0.2CRES + 0.3TO2 + 0.1XO2 |
24.53 |
116 |
|
|
50 |
PHEN (CRES) + OH à 0.4CRO + 0.6(XO2+HO2) + 0.3OPEN |
60.5 |
|
|
|
51 |
XO2 + NO à NO2 |
4.42 |
280 |
|
|
52 |
XO2N + NO à |
4.42 |
280 |
|
|
53 |
XO2 + XO2 à |
0.369 |
190 |
|
|
54 |
XO2 + HO2 à |
0.462 |
800 |
|
|
55 |
XO2N + HO2 à |
0.462 |
800 |
|
|
56 |
XO2N + XO2N à |
0.369 |
190 |
|
|
57 |
XO2N + XO2 à |
0.738 |
190 |
|
|
58 |
SO2 + OH à SULF |
1.5 |
|
|
|
59 |
SO2 à SULF |
See text |
|
|
|
60 |
H2O2 + OH à HO2 |
4.28 |
-160.0 |
|
|
61J |
H2O2 + hv à 2 OH |
|
|
|
|
62J |
HNO3 + hv à OH + NO2 |
|
|
|
|
63 |
HNO3 + OH à NO3 (+ H2O) |
7.58e-3 |
1000.0 |
|
|
64 |
ISO + OH à XO2 + FORM + 0.67HO2 + 0.4MGLY + 0.2C2O3 + ETH + 0.2ALD2 + 0.13XO2N |
1.42e2 |
|
|
|
65 |
ISO + O3 à FORM + 0.4 ALD + 0.55ETH + 0.2MGLY + 0.1PAR + 0.06CO + 0.44 HO2 + 0.1OH |
1.8e-5 |
|
|
|
66 |
ISO + NO3 à XO2N |
0.47 |
|
|
Photolysis reactions
For most of the species the clear sky photolysis rates are calculated according to the Roeths flux algorithm (Poppe et al, 1996).
J = A*exp(B(1-1/cosCθ))
with A the photolysis rate at an overhead sun (θ=0) and C a correction factor to account for the bending of solar radiation through scattering in the atmosphere. The constants A,B,C are given in the following table.
The solar zenith angle q depends on geographical location, i.e. longitude and latitude, local time of day and is calculated with:
t = local time of day
D = 2π(julian
day - 1) / 365
D = 0.006918
- 0.399912 cos(D) + 0.070257 sin(D) -
0.006758
cos(2D) + 0.000907 sin(2D) - 0.002697 cos(3D) +
0.00148
sin(3D)
ss = sin(D)∙
sin(latitude)
cc = cos(D)∙cos(latitude)
cos(q) = ss + cc cos((t - 12.67) ∙ (2 π/ 24)).
|
Nr |
reaction |
A (s-1) |
B |
C |
|
11J |
N2O5 + hv à NO3 + NO2 |
3.79e-5 |
1.70537 |
0.80153 |
|
14J |
HNO2 + hv à OH + NO |
8.96E-04 |
0.99438 |
0.83295 |
|
26J |
FORM + hv à 2 HO2 +CO |
4.05E-05 |
2.06917 |
0.80267 |
|
27J |
FORM + hv à CO |
4.92E-05 |
1.60973 |
0.80184 |
|
31J |
ALD
+ hv à XO2 +2HO2 + CO + FORM |
5.40E-06 |
2.52915 |
0.79722 |
|
62J |
HNO3 + hv à OH + NO2 |
5.48E-07 |
2.86922 |
0.79561 |
|
61J |
H2O2 + hv à 2 OH |
7.78E-06 |
1.91463 |
0.79810 |
For the other photolytic reactions another relation is used:
J = A*exp(B/cosθ)
The constants are given in the following table.
|
Nr |
reaction |
A (s-1) |
B |
|
1J |
NO2 + hv à NO + O3 |
1.45E-02 |
-0.4 |
|
4J |
O3 + hv à a1*O3 + a2*OH |
2.00E-04 |
-1.4 |
|
20J |
NO3 + hv à NO2 + O3 |
1.92E-01 |
-0.059 |
|
21J |
NO3 + hv à NO |
2.43E-02 |
-0.081 |
|
37J |
MGLY + hv à C2O3 + HO2 + CO |
2.90E-04 |
-0.4 |
The photolytic reactions are then corrected with an attenuation factor in case of cloud cover. The amount of clouds in an interval of 3 hours is given in decimals. The attenuation factors are:
|
Fraction sky cover |
Attenuation factor |
|
0.0 (clear) |
1.0 |
|
0.1 |
1.0 |
|
0.2 |
1.0 |
|
0.3 |
0.79 |
|
0.4 |
0.75 |
|
0.5 |
0.72 |
|
0.6 |
0.68 |
|
0.7 |
0.62 |
|
0.8 |
0.53 |
|
0.9 |
0.41 |
|
1.0 (overcast) |
0.35 |