Transcript hno3Columbus.ppt

Agnès Perrin
Improved spectral parameters for HNO3 :
validation of MIPAS satellite measurements
Jean-Marie Flaud, Agnés Perrin,
Laboratoire Interuniversitaire des Systémes Atmosphériques
(LISA), CNRS, Université Paris XII, , France.
F. Mencaraglia, G. Bianchini, A. Boscaleri, B. Carli, S. Ceccherini
Istituto di Fisica Applicata Carrara, Firenze - Italy
G.Brizzi, M.Carlotti, and M.Ridolfi
Dipartimento di Chimica Fisica e inorganica, Bologna, Italy
Ohio State, June 2006
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Outlines
 Improved parameters for HNO3 in the
MIPAS spectral range
• Line positions
• Line intensities
• Line broadening.
 Validation of the HNO3 atmospheric measurements of:
MIPAS on ENVISAT satellite (Michelson Interferometer
for Passive Atmospheric Sounding (@11µm)
 IBEX (Infrared Balloon EXperiment) in the far
infrared (22cm-1).
Ohio State, June 2006
Michelson Interferometer for Passive Atmospheric Sounding
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HNO3 is measured in « real time » using an « operational code » which
MIPAS
is an
high resolution IR FTS spectrometer onboard(26km)
use « limited » microwindows (11µm for HNO3)
the ENVISAT satellite since march 2002
Futur projects: to use more of the informations included in MIPAS spectra
Futur projects: to extend the range of the microwindows
11µm
n5,2n9
8.3µm
.n8+n9
7.6µm
n3, n4
5.8µm
n2
—›MIPAS dedicated Database
J-M.Flaud, C.Piccolo, B.Carli, A.Perrin, L.Coudert, J.L.Teffo, L.Brown,
J. of Atmos. Ocean and Optics, 16, 172-182 (2003).
Ohio State, June 2006
Improved line positions
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11µm (improved)
Cold n5, 2n9 ; Hot n5+n9-n5
8.3µm (weak)
n8+n9 (improved) {n8+n9, n6+n7} (interactions accounted for #)
No change (line positions)
7.6µm {n3,n4} (strong) need to be improved !!!!!
5.8 µm n2
(strong)
#Perrin, Flaud, Keller, Goldman, Blatherwick, Murcray, & Rinsland, J. Mol. Spectr 194 (1999) 113.
Perrin, Orphal, Flaud, Klee, Mellau, Mäder, Walbrodt, Winnewisser, J. Mol. Spect. 228 (2004) 375
Flaud, Piccolo, Carli, Perrin, Coudert, Teffo & Brown ,J. Atmospheric and Ocean Optics, 16 (2003), 172.
Flaud, Perrin, Orphal, Kou, Durkiewick & Piccolo, J.Q.S.R.T. 77 (2003) 355.
Flaud, Brizzi, Carlotti, Perrin, Ridolfi, Atmos. Chem. Phys. Discuss, 6 (2006) 4251
Ohio State, June 2006
#(see paper TG03 by D.Petkie et al.)
Improved HNO3 line intensities
Ohio State, June 2006
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Intensities for the 11 µm bands
.decrease of 14%
Giver et al. J. Opt. Soc. Am. B1, 715 (1984)
Chackerian, Sharpe & Blake, JQSRT 82, 429 (2003)
Toth, Brown & Cohen J.Mol. Spectr 218, 151 (2003)
HIT-2K
HIT-04:
Ohio
State,&June
2006 Rothman et al. JQSRT 82, 5 (2003), 96, 139 (2005)
MIPAS: Flaud et al. Atmos Oceanic Opt. 16, 172 (2003)
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Comparison of observed and simulated MIPAS spectra in band A
for an altitude of 24km
2n9 Q branch
2n9 Q branch
Old database
Ohio State, June 2006
New database
Status of the n3 & n4 bands (7.5µm)
…still unsatisfactory !!!!!!!!!
.n3 Q branch
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.n3 Q branch
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Improved line broadening parameters for HNO3
• Numerous excellent line broadening measurements
were performed mainly in the millimeter wave
spectral range
• Strong rotational dependence of the broadenings
• Sometime, the n- temperature dependance of the
g was also measured.
Goyette T.M., W.L.Ebenstein, F.C. De Lucia and P.Helminger, J. Mol. Spectrosc. 128, (1988) 108.
Goyette T.M., W.Guo, F.C. De Lucia and P.Helminger, J.Q.S.R.T. 46, (1991) 293.
Goyette T.M., E.A.Cohen, and F.De Lucia, J.Q.S.R.T. 60, (1998) 377.
Zu L., P.A.Hamilton and P.B.Davies, J.Q.S.R.T. 73, (2002) 545.
Colmont, Bakri, Rohart, Wlodarczak, J. Mol. Spectr. 220 (2003) 52.
Cazzoli,
Dore,June
Puzzarini,
Ohio State,
2006 Bakri, Colmont, Rohart and Wlodarczak J. Mol. Spect 229 (2005) 158.
Model for HNO3 line broadeningAgnès Perrin
gair(J)= aair + bair.(J’+J’’)
gair in MHz/torr at 296K
Calc
Obs (literature)
5,0
4,8
4,6
4,4
4,2
4,0
3,8
3,6
10
15
20
(J'+J")/2 gair (J)= constant
25
30
35
40
45
Ohio State, June 2006
There
is need for a « correct » model for the broadening….
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Preliminary intercomparison of HNO3 profiles
MIPAS
FTS on ENVISAT
11µm  900cm-1
Line parameters
From HITRAN-2K
IBEX
FTS on a balloon
Far infrared   20cm-1
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Parameters from
JPL catalog
Comparison MIPAS IBEX
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Because of geographical and time dependence of the
atmospheric composition  correlative
measurements should done over the same air mass;
Exact “rendez-vous” satellite  balloon.
Ohio State, June 2006
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Concentration profile of HNO3
MIPAS IBEX
These two profiles desagree….
…………., this may be due to a different
geographical or time dependence of HNO3……..
In our case this required an exact “rendez-vous”
between two moving platforms: satellite and balloon.
….or to spectroscopic problems
inState,
theJune11µm…
(or/and) in the far infrared
Ohio
2006
The pure rotation band for HNO3
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..was updated…in HITRAN-04
HITRAN-04: was updated using the JPL catalog
For the v=0  v=0 (ground  ground) only
Intensities are incorrect for atmospheric uses
(in JPL and …..therefore in HITRAN-04)
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JPL catalog: status of the intensities (@300K)
3
8 
-E”/kT-e-E’/kT)1/Z
2
Int(300K)JPL= 3hc
(e
(T)
|<f'|m
|f">|
40
JPL
0
ZJPL rotation partition function
ZTot(T) =ZRot(T)*ZVib(T)
ZVib(T=300K)1.30
Not accounted for
For Int(T)
this MIPAS
IBEX intercomparison, we
JPL= IntTRUE(T)*ZVib(T=300K)
performed a new calculation of the MW-Far
infrared region forIntensities
HNO3 (ground-ground
hot
overestimated of+ 30%
bands)
(i) best line position parameters
(ii) corrected line intensities
Ohio State,
June 2006 Cohen, Delisky, Pearson & Müller, JQSRT;60, 1998
Picket,
Poynter,
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Final results
11 µm
New line positions
Overall intensities were divided by 1.14
Far infrared (~22cm-1)
New line positions
Overall intensities were divided by1.30
Ohio State, June 2006
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MIPAS: 11µm
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IBEX: Far IR
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Conclusion
 Improved parameters for HNO3 in the MIPAS
spectral range (line positions, line intensities, line
broadening).
 The 7.6µm region need to be updated
Validation of the HNO3 atmospheric measurements of
MIPAS on ENVISAT satellite (@11µm)  IBEX
(Infrared Balloon EXperiment) in the far infrared
(22cm-1).
Ohio State, June 2006
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HITRAN
Sigma
3.00218400
3.00258200
3.00344000
3.00564100
3.00566600
Int
0.108E-23
0.325E-25
0.137E-23
0.165E-23
0.590E-24
3.00206715
3.00207102
3.00214123
3.00218310
3.00223280
3.00258254
3.00300660
3.00343830
3.00423271
3.00426177
3.00466625
3.00471698
3.00507343
3.00529572
3.00564046
0.711E-24
0.159E-25
0.438E-25
0.832E-24
0.956E-25
0.250E-25
0.540E-25
0.105E-23
0.238E-25
0.328E-24
0.166E-24
0.261E-25
0.105E-24
0.477E-25
0.127E-23
#Molecular line parameters for the
v’
v’’
Gr Gr
Gr Gr
Gr Gr
Gr Gr
Gr Gr
V9
V5
V6
Gr
V5
Gr
V6
Gr
V5
V9
V8
V6
V9
V8
Gr
V9
V5
V6
Gr
V5
Gr
V6
Gr
V5
V9
V8
V6
V9
V8
Gr
J’
Ka’ Kc’
21 20
2
6
4
3
23 21
2
29 23
7
40 30 10
19
27
30
21
19
6
28
23
19
24
18
14
33
18
29
13
23
25
20
12
4
23
21
12
19
11
13
24
11
23
7
4
5
2
7
3
6
2
7
6
7
2
9
7
7
J“ Ka“ Kc“
21 19
3
5
5
0
23 20
3
29 22
8
40 29 11
19
27
30
21
19
5
28
23
19
24
18
14
33
18
29
11
22
24
19
12
5
22
20
11
17
11
11
23
10
22
8
5
6
3
8
0
7
3
8
7
8
3
10
8
8
MASTER database”
OhioC.Puzzarini,
State, June 2006
A.Perrin,
J.-M.Colmont, C.Verdes, G.Wlodarczak, G.Cazzoli, S.Buehler, J.-M.Flaud, and
J.Demaison (Journal of Atmospheric Chemistry, in press
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Geographical « rendez-vous »
Ohio State, June 2006
The n5+n9-n9 hot band of HNO3
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Comparison between ATMOS measurements and atmospheric
simulations obtained using the NEW and the OLD database
OLD db
NEW db
J.-M. FLAUD , C. PICCOLO, B. CARLI, A. PERRIN , L. H. COUDERT , J.-L. TEFFO AND L. R.
BROWN,Molecular line parameters for the MIPAS (Michelson Interferometer for Passive Atmospheric
Sounding)
experiment,J. Atmospheric and Ocean Optics, 16, 172-182 (2003)
Ohio State, June 2006
Improvements for MIPAS
iOld parameters
iNew parameters
Ohio State, June 2006
.X2 Error
From P. Raspollini( Private comm.)
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11mm region ( n5 & 2n9 cold bands, n5 +n9-n9 hot bands
=> recent line (positions) improvement (now in MIPAS-PF3.2)
Perrin, Orphal, Flaud, Klee, Mellau, Mäder, Walbrodt, Winnewisser,
J. Mol. Spect. 228 (2004) 375.
Ohio State, June 2006